Method for manufacturing semiconductor device

ABSTRACT

One object of one embodiment of the present invention is to provide a highly reliable semiconductor device including an oxide semiconductor, which has stable electrical characteristics. In a method for manufacturing a semiconductor device, a first insulating film is formed; source and drain electrodes and an oxide semiconductor film electrically connected to the source and drain electrodes are formed over the first insulating film; heat treatment is performed on the oxide semiconductor film so that a hydrogen atom in the oxide semiconductor film is removed; oxygen doping treatment is performed on the oxide semiconductor film, so that an oxygen atom is supplied into the oxide semiconductor film; a second insulating film is formed over the oxide semiconductor film; and a gate electrode is formed over the second insulating film so as to overlap with the oxide semiconductor film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/091,210, filed Apr. 21, 2011, now allowed, which claims the benefitof a foreign priority application filed in Japan as Serial No.2010-100197 on Apr. 23, 2010, both of which are incorporated byreference.

TECHNICAL FIELD

The present invention relates to a semiconductor device and amanufacturing method thereof.

In this specification, a semiconductor device generally means any devicewhich can function by utilizing semiconductor characteristics, and anelectrooptic device, a semiconductor circuit, and electronic equipmentare all semiconductor devices.

BACKGROUND ART

A technique by which transistors are formed using semiconductor thinfilms formed over a substrate having an insulating surface has beenattracting attention. The transistor is applied to a wide range ofelectronic devices such as an integrated circuit (IC) or an imagedisplay device (display device). A silicon-based semiconductor materialis widely known as a material for a semiconductor thin film applicableto the transistor; in addition, an oxide semiconductor has beenattracting attention as another material.

For example, a transistor whose active layer includes an amorphous oxidecontaining indium (In), gallium (Ga), and zinc (Zn) and having anelectron carrier concentration of less than 10¹⁸/cm³ is disclosed (seePatent Document 1).

REFERENCE

-   Patent Document 1: Japanese Published Patent Application No.    2006-165528

DISCLOSURE OF INVENTION

However, when hydrogen or moisture, which forms an electron donor, ismixed into the oxide semiconductor in a process for manufacturing adevice, the electrical conductivity of the oxide semiconductor maychange. Such a phenomenon causes variation in the electricalcharacteristics of a transistor using the oxide semiconductor.

In view of the above problem, one object of one embodiment of thepresent invention is to provide a highly reliable semiconductor deviceincluding an oxide semiconductor, which has stable electricalcharacteristics.

In a process for manufacturing a transistor including an oxidesemiconductor film, dehydration or dehydrogenation treatment throughheat treatment and oxygen doping treatment are performed. In the processfor manufacturing a transistor including an oxide semiconductor film, atleast oxygen doping treatment is performed.

One embodiment of the disclosed invention is a method for manufacturinga semiconductor device, which includes the following steps: a firstinsulating film is formed; source and drain electrodes and an oxidesemiconductor film electrically connected to the source and drainelectrodes are formed over the first insulating film; heat treatment isperformed on the oxide semiconductor film so that a hydrogen atom in theoxide semiconductor film is removed; oxygen doping treatment isperformed on the oxide semiconductor film, so that an oxygen atom issupplied into the oxide semiconductor film; a second insulating film isformed over the oxide semiconductor film; and a gate electrode is formedover the second insulating film so as to overlap with the oxidesemiconductor film.

Another embodiment of the disclosed invention is a method formanufacturing a semiconductor device, which includes the followingsteps: a first insulating film containing an oxygen atom as aconstituent is formed; oxygen doping treatment is performed on the firstinsulating film so that an oxygen atom is supplied into the firstinsulating film; source and drain electrodes and an oxide semiconductorfilm electrically connected to the source and drain electrodes areformed over the first insulating film; heat treatment is performed onthe oxide semiconductor film so that a hydrogen atom in the oxidesemiconductor film is removed; oxygen doping treatment is performed onthe oxide semiconductor film, so that an oxygen atom is supplied intothe oxide semiconductor film; a second insulating film containing anoxygen atom as a constituent is formed over the oxide semiconductorfilm; oxygen doping treatment is performed on the second insulating filmso that an oxygen atom is supplied into the second insulating film; anda gate electrode is formed over the second insulating film so as tooverlap with the oxide semiconductor film.

In the above, the oxide semiconductor film may be subjected to dopingtreatment to contain an oxygen atom whose proportion is greater than thestoichiometric proportion of the oxide semiconductor film and less thantwice the stoichiometric proportion. Further, an insulating filmcontaining a constituent element of the oxide semiconductor film may beformed as the first insulating film or the second insulating film.Alternatively, an insulating film containing a constituent element ofthe oxide semiconductor film and a film containing an element differentfrom a constituent element of the insulating film may be formed as thefirst insulating film or the second insulating film. An insulating filmcontaining a gallium oxide may be formed as the first insulating film orthe second insulating film. Alternatively, an insulating film containinga gallium oxide and a film containing a material different from agallium oxide may be formed as the first insulating film or the secondinsulating film. The term “gallium oxide” in this specification refersto oxygen and gallium as constituent elements unless otherwiseparticularly specified, and is not limited to only a gallium oxide. Forexample, “an insulating film containing a gallium oxide” can also beregarded as “an insulating film containing oxygen and gallium”.

Further, in the above structure, an insulating film containing nitrogenmay be formed so as to cover the gate electrode. In the case where aninsulating film includes silicon nitride or the like which does notcontain hydrogen or contains an extremely small amount of hydrogen isused, oxygen which is added can be prevented from being released to theoutside, and further, entry of hydrogen or water from the outside can beprevented. In this way, the insulating film is important.

Note that the above-described “oxygen doping” means that oxygen (whichincludes at least one of an oxygen radical, an oxygen atom, and anoxygen ion) is added to a bulk. Note that the term “bulk” is used inorder to clarify that oxygen is added not only to a surface of a thinfilm but also to the inside of the thin film. In addition, “oxygendoping” includes “oxygen plasma doping” in which oxygen which is made tobe plasma is added to a bulk.

By the oxygen doping treatment, oxygen whose amount is greater than thestoichiometric proportion exists in at least one of the oxidesemiconductor film (a bulk thereof), the insulating film (a bulkthereof), and an interface between the oxide semiconductor film and theinsulating film. The amount of oxygen is preferably greater than thestoichiometric proportion and less than four times the stoichiometricproportion, more preferably greater than the stoichiometric proportionand less than twice the stoichiometric proportion. Here, an oxidecontaining excessive oxygen whose amount is greater than thestoichiometric proportion refers to, for example, an oxide whichsatisfies 2g>3a+3b+2c+4d+3e+2f, where the oxide is expressed byIn_(a)Ga_(b)Zn_(c)Si_(d)Al_(e)Mg_(f)O_(g) (a, b, c, d, e, f, g≧0). Notethat oxygen which is added by the oxygen doping treatment may existbetween lattices of the oxide semiconductor.

In addition, oxygen is added so that the amount of the added oxygen islarger than at least the amount of hydrogen in the oxide semiconductorsubjected to dehydration or dehydrogenation. When the amount of oxygenis larger in at least any of the above structures, the oxygen isdiffused and reacts with hydrogen which causes instability, so thathydrogen can be fixed (can be ionized to be an immobile ion). In otherwords, instability in reliability can be reduced or sufficientlyreduced. In addition, with excessive oxygen, variation in a thresholdvoltage Vth caused by oxygen deficiency can be reduced and the amount ofthreshold voltage shift ΔVth can be reduced.

Note that oxygen whose amount is equal to the above-described amountpreferably exists in two or more of the oxide semiconductor film (thebulk), the insulating film (the bulk), and the interface between theoxide semiconductor film and the insulating film.

Note that while it is acceptable that the amount of oxygen is equal tothe stoichiometric proportion in a defect (oxygen deficiency)-free oxidesemiconductor, in order to secure reliability, for example, to suppressvariation in the threshold voltage of a transistor, it is preferablethat an oxide semiconductor contain oxygen whose amount is greater thanthe stoichiometric proportion. Similarly, while the base film is notnecessarily an insulating film containing excessive oxygen in the caseof a defect (oxygen deficiency)-free oxide semiconductor, in order tosecure reliability, for example, to suppress variation in the thresholdvoltage of a transistor, it is preferable that the base film be aninsulating film containing excessive oxygen, considering the possibilityof occurrence of oxygen deficiency in the oxide semiconductor layer.

Here, a state in which oxygen is added to the bulk by theabove-described “oxygen plasma doping” treatment is described. Note thatwhen oxygen doping treatment is performed on an oxide semiconductor filmcontaining oxygen as one constituent, it is generally difficult to checkan increase or a decrease of the oxygen concentration. Therefore, here,an effect of oxygen doping treatment was confirmed with a silicon wafer.

Oxygen doping treatment was performed with the use of an inductivelycoupled plasma (ICP) method. Conditions thereof were as follows: the ICPpower is 800 W; the RF bias power 300 W or 0 W; the pressure 1.5 Pa; thegas flow of oxygen rate 75 sccm; and the substrate temperature 70° C.FIG. 15 shows an oxygen concentration profile in the depth direction ofthe silicon wafer according to secondary ion mass spectrometry (SIMS)measurement. In FIG. 15, the vertical axis indicates an oxygenconcentration; the horizontal axis indicates a depth from a surface ofthe silicon wafer.

It can be confirmed from FIG. 15 that oxygen is added in either of caseswhere the RF bias power is 0 W or the RF bias power is 300 W. Inaddition, in the case where the RF bias power is 300 W, oxygen is addedmore deeply than in the case of the RF bias power of 0 W.

Next, FIGS. 16A and 16B show results of observation of a cross sectionof the silicon wafer which has not yet been subjected to oxygen dopingtreatment and has been subjected to oxygen doping treatment, accordingto scanning transmission electron microscopy (STEM). FIG. 16A is a STEMimage of the silicon wafer which has not yet been subjected to oxygendoping treatment. FIG. 16B is a STEM image of the silicon wafer whichhas been doped with oxygen at the RF bias power of 300 W. Referring toFIG. 16B, it can be confirmed that an oxygen-highly-doped region isformed in the silicon wafer by the oxygen doping.

As described above, it is shown that oxygen is added to the siliconwafer by doping the silicon wafer with oxygen. This result leads to anunderstanding that it is natural that oxygen can also be added to anoxide semiconductor film by doping the oxide semiconductor film withoxygen.

The effect of the structure which is an embodiment of the disclosedinvention can be easily understood by considering as below. Thedescription below is just one exemplary consideration.

When a positive voltage is applied to the gate electrode, an electricfield is generated from the gate electrode side of the oxidesemiconductor film to the back channel side (the side opposite to thegate insulating film), and accordingly, hydrogen ions having positivecharge which exist in the oxide semiconductor film are transferred tothe back channel side, and accumulated in the oxide semiconductor filmside of an interface between the oxide semiconductor film and theinsulating film. The positive charge is transferred from the accumulatedhydrogen ion to a charge trapping center (such as a hydrogen atom,water, or contamination) in the insulating film, whereby negative chargeis accumulated in the back channel side of the oxide semiconductor film.In other words, a parasitic channel is generated on the back channelside of the transistor, and the threshold voltage is shifted to thenegative side, so that the transistor tends to be normally on.

In this manner, the charge trapping center such as hydrogen or water inthe insulating film traps the positive charge and is transferred intothe insulating film, which varies electrical characteristics of thetransistor. Therefore, in order to suppress variation of the electricalcharacteristics of the transistor, it is important that there is nocharge trapping center or the number of charge trapping centers is smallin the insulating film. Therefore, a sputtering method by which lesshydrogen is contained in film deposition is desirably used for formationof the insulating film. In an insulating film deposited by thesputtering method, there is no charge trapping center or the number ofwhich is small, and thus, the transfer of positive charge is less likelyto occur as compared to the case deposition is performed using a CVDmethod or the like. Accordingly, the shift of the threshold voltage ofthe transistor can be suppressed and the transistor can be normally off.

Note that in a top-gate transistor, when an oxide semiconductor film isformed over an insulating film serving as a base and then heat treatmentis performed thereon, not only water or hydrogen contained in the oxidesemiconductor film but also water or hydrogen contained in theinsulating film can be removed. Accordingly, in the insulating film,there is a small number of charge trapping centers for trapping positivecharge transferred through the oxide semiconductor film. In this manner,the heat treatment for dehydration or dehydrogenation is also performedon the insulating film located below the oxide semiconductor film, inaddition to the oxide semiconductor film. Therefore, in the top-gatetransistor, the insulating film serving as a base may be formed by a CVDmethod such as a plasma CVD method.

On the other hand, when a negative voltage is applied to the gateelectrode, an electric field is generated from the back channel side tothe gate electrode side, and accordingly, hydrogen ions which exist inthe oxide semiconductor film are transferred to the gate insulating filmside and are accumulated in the oxide semiconductor film side of theinterface between the oxide semiconductor film and the gate insulatingfilm. As a result, the threshold voltage of the transistor is shifted tothe negative side.

In a state of application of a voltage of 0, the positive charge isreleased from the charge trapping center, so that the threshold voltageof the transistor is shifted to the positive side, thereby returning tothe initial state, or the threshold voltage is shifted to the positiveside beyond the initial state in some cases. These phenomena indicatethe existence of easy-to-transfer ions in the oxide semiconductor film.It can be considered that an ion that is transferred most easily is ahydrogen ion that is the smallest atom.

In addition, the oxide semiconductor film absorbs light, whereby a bondof a metal element (M) and a hydrogen atom (H) (the bond also referredto as an M—H bond) in the oxide semiconductor film is cut by opticalenergy. Note that the optical energy having a wavelength of about 400 nmis equal to or substantially equal to the bond energy of a metal elementand a hydrogen atom. When a negative gate bias is applied to atransistor in which the bond of a metal element and a hydrogen atom inthe oxide semiconductor film is cut, a hydrogen ion detached from themetal element is attracted to the gate electrode side, so thatdistribution of electrical charge is changed, the threshold voltage ofthe transistor is shifted to the negative side, and the transistor tendsto be normally on.

Note that the hydrogen ions transferred to the interface of the gateinsulating film by light irradiation and application of the negativegate bias to the transistor are returned to the initial state bystopping application of the voltage. This can be regarded as a typicalexample of the ion transfer in the oxide semiconductor film.

In order to prevent such a change of the electrical characteristics byvoltage application (BT deterioration) or a change of the electricalcharacteristics by light irradiation (light deterioration), it isimportant to remove a hydrogen atom or an impurity containing a hydrogenatom such as water thoroughly from the oxide semiconductor film tohighly purify the oxide semiconductor film. The charge density as smallas 10¹⁵ cm⁻³, or the charge per unit area as small as 10¹⁰ cm⁻² does notaffect the transistor characteristics or very slightly affects them.Therefore, it is preferable that the charge density is less than orequal to 10¹⁵ cm⁻³. Assuming that 10% of hydrogen contained in the oxidesemiconductor film is transferred within the oxide semiconductor film,it is preferable that the hydrogen concentration is less than or equalto 10¹⁶ cm⁻³. Further, in order to prevent entry of hydrogen from theoutside after a device is completed, it is preferable that a siliconnitride film formed by a sputtering method is used as a passivation filmto cover the transistor.

Hydrogen or water can also be removed from the oxide semiconductor filmby doping with oxygen which is excessive as compared to hydrogencontained in the oxide semiconductor film (such that (the number ofhydrogen atoms)<<(the number of oxygen radicals) or (the number ofoxygen ions)). Specifically, oxygen is made to be plasma by aradio-frequency wave (RF), the bias of the substrate is increased, andan oxygen radical and/or an oxygen ion are/is doped or added into theoxide semiconductor film over the substrate such that the amount ofoxygen is greater than that of hydrogen in the oxide semiconductor film.The electronegativity of oxygen is 3.0 which is larger than about 2.0,the electronegativity of a metal (Zn, Ga, In) in the oxide semiconductorfilm, and thus, oxygen contained excessively as compared to hydrogendeprives the M-H group of a hydrogen atom, so that an OH group isformed. This OH group may form an M—O—H group by being bonded to M.

The oxygen doping is preferably performed such that the amount of oxygenin the oxide semiconductor film is greater than the stoichiometricproportion of the oxide semiconductor film. For example, in the casewhere an In—Ga—Zn—O-based oxide semiconductor film is used as the oxidesemiconductor film, it is far preferable that the proportion of oxygenbe made to be greater than the stoichiometric proportion of the oxidesemiconductor film and less than twice the stoichiometric proportion byoxygen doping or the like. For example, when a single-crystalIn—Ga—Zn—O-based oxide semiconductor has the following stoichiometricproportion: In:Ga:Zn:O=1:1:1:4, in a thin oxide semiconductor film whosecomposition is expressed by InGaZnO_(x), x is further preferably greaterthan 4 and less than 8.

Optical energy or BT stress detaches a hydrogen ion from the M-H group,which causes deterioration; however, in the case where oxygen is addedby the above-described doping, added oxygen is bonded with a hydrogenion, so that an OH group is formed. The OH group does not discharge ahydrogen ion even by light irradiation of the transistor or applicationof BT stress on the transistor because of its high bond energy, and isnot easily transferred through the oxide semiconductor film because ofits mass greater than the mass of a hydrogen ion. Accordingly, an OHgroup formed by oxygen doping does not cause deterioration of thetransistor or can suppress the deterioration.

In addition, it has been confirmed that as the thickness of the oxidesemiconductor film is increased, the variation in the threshold voltageof a transistor tends to increase. It can be guessed that this isbecause an oxygen defect in the oxide semiconductor film is one cause ofthe change of the threshold voltage and increases as the thickness ofthe oxide semiconductor film is increased. A step of doping an oxidesemiconductor film with oxygen in a transistor according to oneembodiment of the present invention is effective not only for removal ofhydrogen or water from the oxide semiconductor film but also forcompensation of an oxygen defect in the film. Accordingly, the variationin the threshold voltage can also be controlled in the transistoraccording to one embodiment of the present invention.

Metal oxide films each formed of a constituent similar to that of theoxide semiconductor film may be provided so as to sandwich the oxidesemiconductor film, which is also effective for prevention of change ofthe electrical characteristics. As the metal oxide film formed of aconstituent similar to that of the oxide semiconductor film,specifically, a film containing at least one selected from theconstituent elements of the oxide semiconductor film is preferably used.Such a material is compatible with the oxide semiconductor film, andtherefore, when the metal oxide films are provided so as to sandwich theoxide semiconductor film, the state of the interface between with theoxide semiconductor film can be kept well. That is, by providing themetal oxide film using the above-described material as an insulatingfilm which is in contact with the oxide semiconductor film, accumulationof hydrogen ions at the interface between the metal oxide film and theoxide semiconductor film and in the vicinity thereof can be suppressedor prevented. Thus, as compared to the case where insulating films eachformed of a different constituent from the oxide semiconductor film,such as silicon oxide films are provided so as to sandwich the oxidesemiconductor film, the hydrogen concentration at the interface of theoxide semiconductor film, which affects the threshold voltage of thetransistor, can be sufficiently decreased.

Gallium oxide films are preferably used as the metal oxide films. Sincea gallium oxide has a wide bandgap (Eg), by providing gallium oxidefilms so as to sandwich the oxide semiconductor film, an energy barrieris formed at the interface between the oxide semiconductor film and themetal oxide film to prevent carrier transport in the interface.Consequently, carriers do not travel from the oxide semiconductor to themetal oxide, but travels through the oxide semiconductor film. On theother hand, hydrogen ions pass through the interface between the oxidesemiconductor and the metal oxide and are accumulated in the vicinity ofthe interface between the metal oxide and the insulating film. Even whenthe hydrogen ions are accumulated in the vicinity of the interface withthe insulating film, a parasitic channel through which carriers can flowis not formed in the metal oxide film such as a gallium oxide film,which results in no affect or a very slight affect on the thresholdvoltage of the transistor. The energy barrier in the case where agallium oxide is in contact with an In—Ga—Zn—O-based material is about0.8 eV on the conduction band side and is about 0.9 eV on the valenceband side.

One technological idea of a transistor according to one embodiment ofthe disclosed invention is to increase the amount of oxygen contained inat least one of an insulating film in contact with an oxidesemiconductor film, the oxide semiconductor film, and the vicinity of aninterface between them by oxygen doping treatment.

In the case where an oxide semiconductor material which contains indiumwhose bonding strength to oxygen is relatively weak is used for theoxide semiconductor film, when the insulating film in contact with theoxide semiconductor film contains a material which has a strongerbonding strength to oxygen, such as silicon, oxygen in the oxidesemiconductor film may be extracted by heat treatment, which may causeformation of oxygen deficiency in the vicinity of the interface of theoxide semiconductor film. However, in a transistor according to oneembodiment of the disclosed invention, formation of oxygen deficiencycan be suppressed by supplying excessive oxygen to the oxidesemiconductor film.

Here, after the oxygen doping is performed in the manufacturing processof a transistor, the amount of oxygen which is greater than thestoichiometric proportion and is contained in the oxide semiconductorfilm or the insulating film in contact with the oxide semiconductor filmmay be different between layers. It can be considered that chemicalpotential of oxygen is different between the layers between which theamount of excessive oxygen is different, and the state where thechemical potential is different reaches an equilibrium state or asubstantial equilibrium state by heat treatment or the like from in themanufacturing process of the transistor. Distribution of oxygen in theequilibrium state is considered below.

The equilibrium state at a temperature T at a pressure P refers to thestate in which a Gibbs free energy of the whole of the systems G is theminimum, which is represented by the following formula (1).

[FORMULA 1]

G(N _(a) ,N _(b) ,N _(c) , . . . ,T,P)=G ⁽¹⁾(N _(a) ,N _(b) ,N _(c) , .. . ,T,P)+G ⁽²⁾(N _(a) ,N _(b) ,N _(c) , . . . ,T,P)+G ⁽³⁾(N _(a) ,N_(b) ,N _(c) , . . . ,T,P)  (1)

In the formula (1), reference symbols G⁽¹⁾, G⁽²⁾, and G⁽³⁾ denote Gibbsfree energies of layers. N_(a), N_(b), and N_(c) denote the number ofparticles, and reference symbols a, b, and c denote particle kinds. Thechange of the Gibbs free energy is represented by the following formula(2) when the particle a is transferred from an i layer to a j layer byδ_(a) ^((j)).

$\begin{matrix}\left\lbrack {{FORMULA}\mspace{14mu} 2} \right\rbrack & \; \\{{\delta \; G} = {{{- \frac{\partial G^{(i)}}{\partial N_{a}^{(i)}}}\delta \; N_{a}^{(j)}} + {\frac{\partial G^{(j)}}{\partial N_{a}^{(j)}}\delta \; N_{a}^{(j)}}}} & (2)\end{matrix}$

When δG is 0 in the formula (2), that is, when the following formula (3)is satisfied, the system is in the equilibrium state.

$\begin{matrix}\left\lbrack {{FORMULA}\mspace{14mu} 3} \right\rbrack & \; \\{\frac{\partial G^{(i)}}{\partial N_{a}^{(i)}} = \frac{\partial G^{(j)}}{\partial N_{a}^{(j)}}} & (3)\end{matrix}$

The derivative of the Gibbs free energy with respect to the number ofparticles corresponds to the chemical potential, and thus the chemicalpotentials of particles are uniform in the layers in the equilibriumstate.

In other words, specifically, when the amount of oxygen contained in theoxide semiconductor film is excessive as compared to the insulatingfilm, the chemical potential of oxygen is relatively low in theinsulating film and is relatively high in the oxide semiconductor film.

Then, when the temperature of the whole of the systems (here, the oxidesemiconductor film and the insulating film in contact with the oxidesemiconductor film) becomes high enough to cause atom diffusion in thelayer and between the layers by heat treatment in the manufacturingprocess of the transistor, oxygen is transferred so as to make thechemical potentials uniform. That is, oxygen in the oxide semiconductorfilm is transferred to the insulating film, whereby the chemicalpotential of the oxide semiconductor film is decreased and the chemicalpotential of the insulating film is increased.

Therefore, oxygen supplied excessively to the oxide semiconductor filmby the oxygen doping treatment is diffused to be supplied to theinsulating film (including the interface) by the following heattreatment to make the chemical potential to be in the equilibrium state.Thus, when the oxide semiconductor film contains excessive oxygen,oxygen can also be excessively contained in the insulating film(including the interface) in contact with the oxide semiconductor film.

Thus, it can be said that it is highly significant that oxygen besupplied into the oxide semiconductor film so that the amount of oxygenis large enough to compensate oxygen deficiency in the insulating filmor at the interface with the insulating film (the amount of oxygen issuch that a surplus is left even after compensation of oxygendeficiency).

A transistor including an oxide semiconductor film subjected todehydration or dehydrogenation by heat treatment and oxygen dopingtreatment can be a highly reliable transistor having stable electricalcharacteristics in which the amount of change in threshold voltage ofthe transistor between before and after the bias-temperature stress (BT)test can be reduced.

According to one embodiment of the disclosed invention, a variety ofsemiconductor devices including highly reliable transistors havingfavorable electrical characteristic can be manufactured.

BRIEF DESCRIPTION OF DRAWINGS

In the accompanying drawings:

FIGS. 1A to 1C illustrate an embodiment of a semiconductor device;

FIGS. 2A to 2G illustrate an embodiment of a method for manufacturing asemiconductor device;

FIGS. 3A to 3D each illustrate an embodiment of a semiconductor device;

FIGS. 4A to 4F illustrate an embodiment of a method for manufacturing asemiconductor device;

FIGS. 5A to 5C illustrate the embodiment of a method for manufacturing asemiconductor device;

FIGS. 6A to 6F illustrate an embodiment of a method for manufacturing asemiconductor device;

FIGS. 7A to 7C are a cross-sectional view, a top view, and a circuitdiagram of a semiconductor device, respectively;

FIGS. 8A to 8C each illustrate an embodiment of a semiconductor device;

FIG. 9 illustrates an embodiment of a semiconductor device;

FIG. 10 illustrates an embodiment of a semiconductor device;

FIG. 11 illustrates an embodiment of a semiconductor device;

FIGS. 12A and 12B illustrate an embodiment of a semiconductor device;

FIGS. 13A and 13B illustrate an electronic appliance;

FIGS. 14A to 14F illustrate electronic appliances;

FIG. 15 shows measurement results of SIMS;

FIGS. 16A and 16B are cross-sectional STEM images; and

FIGS. 17A and 17B are a top view and a cross-sectional view of a plasmaapparatus.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the invention disclosed in thisspecification will be described in detail with reference to theaccompanying drawings. The present invention is not limited to thefollowing description, and it is easily understood by those skilled inthe art that modes and details of the present invention can be modifiedin various ways. Accordingly, the invention disclosed in thisspecification is not construed as being limited to the description ofthe embodiments included herein.

In this specification and the like, ordinal numbers such as “first”,“second”, and “third” are used in order to avoid confusion amongcomponents, and the terms do not limit the components numerically.

Embodiment 1

In this embodiment, a semiconductor device and a manufacturing methodthereof will be described with reference to FIGS. 1A to 1C, FIGS. 2A to2G, and FIGS. 3A to 3D.

<Structural Example of Semiconductor Device>

FIGS. 1A to 1C illustrate a structural example of a transistor 120.Here, FIG. 1A is a plan view, FIG. 1B is a cross-sectional view alongA-B of FIG. 1A, and FIG. 1C is a cross-sectional view along C-D of FIG.1A. Note that some of components of the transistor 120 (e.g., a gateinsulating film 110) are omitted in FIG. 1A for brevity.

The transistor 120 in FIGS. 1A to 1C includes, over a substrate 100, aninsulating film 102, a source electrode 104 a, a drain electrode 104 b,an oxide semiconductor film 108, the gate insulating film 110, and agate electrode 112.

In the transistor 120 in FIGS. 1A to 1C, the oxide semiconductor film108 has been subjected to the oxygen doping treatment. The oxygen dopingtreatment enables higher reliability of the transistor 120.

<Example of Manufacturing Process of Semiconductor Device>

An example of a manufacturing process of the semiconductor device inFIGS. 1A to 1C will be described below with reference to FIGS. 2A to 2G.

First, the insulating film 102 is formed over the substrate 100 (seeFIG. 2A).

There is no particular limitation on the property of a material and thelike of the substrate 100 as long as the material has heat resistancehigh enough to withstand at least heat treatment performed later. Forexample, a glass substrate, a ceramic substrate, a quartz substrate, ora sapphire substrate can be used as the substrate 100. Alternatively, asingle crystal semiconductor substrate or a polycrystallinesemiconductor substrate made of silicon, silicon carbide, or the like, acompound semiconductor substrate made of silicon germanium or the like,an SOI substrate, or the like may be used as the substrate 100. Stillalternatively, any of these substrates further provided with asemiconductor element may be used as the substrate 100.

A flexible substrate may alternatively be used as the substrate 100.When a transistor is provided over the flexible substrate, thetransistor may be directly formed over the flexible substrate, or thetransistor may be formed over a different substrate and then separatedto be transferred to the flexible substrate. In order to separate thetransistor to transfer it to the flexible substrate, a separation layeris preferably formed between the different substrate and the transistor.

The insulating film 102 serves as a base. Specifically, the insulatingfilm 102 may be formed using a silicon oxide, a silicon nitride, analuminum oxide, an aluminum nitride, a gallium oxide, a mixed materialthereof, or the like. The insulating film 102 may have a single-layerstructure or a stacked structure using an insulating film including anyof the above materials.

There is no particular limitation on the method for forming theinsulating film 102. For example, the insulating film 102 may be formedby a deposition method such as a plasma CVD method or a sputteringmethod. A sputtering method is preferable in terms of low possibility ofentry of hydrogen, water, and the like.

Note that it is particularly preferable to form the insulating film 102with the use of an insulating material containing a constituent similarto that of an oxide semiconductor film formed later. Such a material iscompatible with an oxide semiconductor film; thus, when it is used forthe insulating film 102, the state of the interface with the oxidesemiconductor film can be kept favorably. Here, “a constituent similarto that of an oxide semiconductor film” means one or more of elementsselected from constituent elements of the oxide semiconductor film. Forexample, in the case where the oxide semiconductor film is formed usingan In—Ga—Zn—O-based oxide semiconductor material, a gallium oxide or thelike is given as such an insulating material containing a constituentsimilar to that of the oxide semiconductor film.

In the case where the insulating film 102 has a stacked structure, it isfurther preferable to employ a stacked structure of a film formed usingan insulating material containing a constituent similar to that of theoxide semiconductor film (hereinafter referred to as a film a) and afilm containing a material different from that of a constituent materialof the film a (hereinafter referred to as a film b). The reason is asfollows. When the insulating film 102 has such a structure in which thefilm a and the film b are sequentially stacked on the oxidesemiconductor film side, charge is trapped preferentially in a chargetrapping center at the interface between the film a and the film b(compared with the interface between the oxide semiconductor film andthe film a). Thus, trapping of charge at the interface of the oxidesemiconductor film can be sufficiently suppressed, resulting in higherreliability of the semiconductor device.

Note that as such a stacked structure, a stack of a gallium oxide filmand a silicon oxide film, a stack of a gallium oxide film and a siliconnitride film, or the like may be used.

Next, a conductive film for forming the source electrode and the drainelectrode (including a wiring formed in the same layer as the sourceelectrode and the drain electrode) is formed over the insulating film102 and processed to form the source electrode 104 a and the drainelectrode 104 b (see FIG. 2B). The channel length L of the transistor isdetermined by the distance between the edges of the source electrode 104a and the drain electrode 104 b which are formed here.

As the conductive film used for the source electrode 104 a and the drainelectrode 104 b, a metal film containing an element selected from Al,Cr, Cu, Ta, Ti, Mo, and W, a metal nitride film containing any of theabove elements as its constituent (e.g., a titanium nitride film, amolybdenum nitride film, or a tungsten nitride film), or the like may beused. Alternatively, a conductive film may be used in which ahigh-melting-point metal film of Ti, Mo, W, or the like or a metalnitride film of any of these elements (a titanium nitride film, amolybdenum nitride film, or a tungsten nitride film) may be stacked onone of or both a bottom side and a top side of a metal film of Al, Cu,or the like.

Alternatively, the conductive film used for the source electrode 104 aand the drain electrode 104 b may be formed using a conductive metaloxide. As the conductive metal oxide, an indium oxide (In₂O₃), a tinoxide (SnO₂), a zinc oxide (ZnO), an indium oxide-tin oxide alloy(In₂O₃—SnO₂, which is abbreviated to ITO), an indium oxide-zinc oxidealloy (In₂O₃—ZnO), or any of these metal oxide materials containing asilicon oxide may be used.

The conductive film may be processed by etching with the use of a resistmask. Ultraviolet, a KrF laser light, an ArF laser light, or the like ispreferably used for light exposure for forming a resist mask for theetching.

In the case where the channel length L is less than 25 nm, the lightexposure at the time of forming the resist mask is preferably performedusing, for example, extreme ultraviolet having an extremely shortwavelength of several nanometers to several tens of nanometers. In thelight exposure using extreme ultraviolet, the resolution is high and thefocus depth is large. Thus, the channel length L of the transistorformed later can be reduced, whereby the operation speed of a circuitcan be increased.

An etching step may be performed with the use of a resist mask formedusing a so-called multi-tone mask. A resist mask formed using amulti-tone mask has a plurality of thicknesses and can be furtherchanged in shape by ashing; thus, such a resist mask can be used in aplurality of etching steps for different patterns. Therefore, a resistmask for at least two kinds of patterns can be formed using a multi-tonemask, resulting in simplification of the process.

Next, an oxide semiconductor film is formed over the insulating film 102and in contact with the source electrode 104 a and the drain electrode104 b and then is processed to form an oxide semiconductor film 106having an island shape (see FIG. 2C).

The oxide semiconductor film is desirably formed by a method by whichhydrogen, water, and the like do not easily enter the film, such as asputtering method. The thickness of the oxide semiconductor film isdesirably larger than or equal to 3 nm and smaller than or equal to 30nm. This is because the transistor might possibly be normally on whenthe oxide semiconductor film is too thick (e.g., the thickness is 50 nmor more).

As a material of the oxide semiconductor film, for example, an oxidesemiconductor material containing indium or an oxide semiconductormaterial containing indium and gallium may be used.

As a material of the oxide semiconductor film, any of the followingmaterials can be used: a four-component metal oxide such as anIn—Sn—Ga—Zn—O-based material; three-component metal oxides such as anIn—Ga—Zn—O-based material, an In—Sn—Zn—O-based material, anIn—Al—Zn—O-based material, a Sn—Ga—Zn—O-based material, anAl—Ga—Zn—O-based material, and a Sn—Al—Zn—O-based material;two-component metal oxides such as an In—Zn—O-based material, aSn—Zn—O-based material, an Al—Zn—O-based material, a Zn—Mg—O-basedmaterial, a Sn—Mg—O-based material, an In—Mg—O-based material, and anIn—Ga—O-based material; and single-component metal oxides such as anIn—O-based material, a Sn—O-based material, and a Zn—O-based material.In addition, the above materials may contain silicon oxide. Here, forexample, an In—Ga—Zn—O-based material means an oxide film containingindium (In), gallium (Ga), and zinc (Zn), and there is no particularlimitation on the composition ratio thereof. Further, theIn—Ga—Zn—O-based material may contain another element in addition to In,Ga, and Zn.

The oxide semiconductor film may be a thin film formed using a materialexpressed by the chemical formula, InMO₃(ZnO)_(m) (m>0). Here, Mrepresents one or more metal elements selected from Ga, Al, Mn, and Co.For example, M may be Ga, Ga and Al, Ga and Mn, Ga and Co, or the like.

In the case where an In—Zn—O-based material is used for the oxidesemiconductor film, a target with the following composition ratio isused: the composition ratio of In:Zn is 50:1 to 1:2 in an atomic ratio(In₂O₃:ZnO=25:1 to 1:4 in a molar ratio), preferably 20:1 to 1:1 in anatomic ratio (In₂O₃:ZnO=10:1 to 1:2 in a molar ratio), furtherpreferably 15:1 to 1.5:1 in an atomic ratio (In₂O₃:ZnO=15:2 to 3:4 in amolar ratio). For example, a target used for the formation of anIn—Zn—O-based oxide semiconductor has the following atomic ratio: theatomic ratio of In:Zn:O is X:Y:Z, where Z>1.5X+Y.

In this embodiment, the oxide semiconductor film is formed by asputtering method using an In—Ga—Zn—O-based oxide semiconductordeposition target.

As the In—Ga—Zn—O-based oxide semiconductor deposition target, forexample, an oxide semiconductor deposition target with the followingcomposition ratio may be used: In₂O₃:Ga₂O₃:ZnO=1:1:1 [molar ratio]. Notethat it is not necessary to limit the material and the composition ratioof the target to the above. For example, an oxide semiconductordeposition target with the following composition ratio may alternativelybe used: In₂O₃:Ga₂O₃:ZnO=1:1:2 [molar ratio].

The fill rate of the oxide semiconductor deposition target is higherthan or equal to 90% and lower than or equal to 100%, preferably, higherthan or equal to 95% and lower than or equal to 99.9%. With the use ofthe oxide semiconductor deposition target with high fill rate, a denseoxide semiconductor film can be formed.

The deposition atmosphere may be a rare gas (typically argon)atmosphere, an oxygen atmosphere, or a mixed atmosphere containing arare gas and oxygen. Moreover, it is desirably an atmosphere using ahigh-purity gas in which impurities containing hydrogen atoms, such ashydrogen, water, a hydroxyl group, and hydride, are removed becauseentry of hydrogen, water, a hydroxyl group, and hydride into the oxidesemiconductor film can be prevented.

More specifically, for example, the oxide semiconductor film can beformed as follows.

First, the substrate 100 is placed in a deposition chamber kept underreduced pressure, and the substrate temperature is set to a temperaturehigher than or equal to 100° C. and lower than or equal to 600° C.,preferably higher than or equal to 200° C. and lower than or equal to400° C. This is because the concentration of an impurity contained inthe oxide semiconductor film can be reduced when deposition is performedwhile the substrate 100 is heated. This is also because damage to theoxide semiconductor film due to sputtering can be reduced.

Then, a high-purity gas in which impurities containing hydrogen atoms,such as hydrogen and moisture, are sufficiently removed is introducedinto the deposition chamber from which remaining moisture is beingremoved, and the oxide semiconductor film is formed over the substrate100 with the use of the target. To remove moisture remaining in thedeposition chamber, an entrapment vacuum pump such as a cryopump, an ionpump, or a titanium sublimation pump is desirably used as an evacuationmeans. Further, an evacuation means may be a turbo molecular pumpprovided with a cold trap. In the deposition chamber which is evacuatedwith the cryopump, a hydrogen molecule, a compound containing a hydrogenatom, such as water (H₂O), (further preferably, also a compoundcontaining a carbon atom), and the like are removed, whereby theconcentration of an impurity in the oxide semiconductor film formed inthe deposition chamber can be reduced.

An example of the deposition condition is as follows: the distancebetween the substrate and the target is 100 mm, the pressure is 0.6 Pa,the direct-current (DC) power is 0.5 kW, and the deposition atmosphereis an oxygen atmosphere (the flow rate of the oxygen is 100%). Note thata pulse direct current power source is preferable because generation ofpowdery substances (also referred to as particles or dust) in depositioncan be reduced and unevenness in film thickness can be reduced.

The oxide semiconductor film can be processed by being etched after amask having a desired shape is formed over the oxide semiconductor film.The mask may be formed by a method such as photolithography or an inkjet method.

For the etching of the oxide semiconductor film, either wet etching ordry etching may be employed. It is needless to say that both of them maybe employed in combination.

After that, heat treatment is performed on the oxide semiconductor film106 so that the highly-purified oxide semiconductor film 108 is formed(see FIG. 2D). Hydrogen (including water and a hydroxyl group) in theoxide semiconductor film 106 is removed through the heat treatment andthe structure of the oxide semiconductor film is modified, so thatdefect levels in an energy gap can be reduced. The heat treatment isperformed at a temperature of higher than or equal to 250° C. and lowerthan or equal to 650° C., preferably higher than or equal to 450° C. andlower than or equal to 600° C. The temperature of the heat treatment ispreferably lower than the strain point of the substrate.

The heat treatment may be performed, for example, in such a manner thatan object to be processed is introduced into an electric furnace inwhich a resistance heating element or the like is used and heated in anitrogen atmosphere at 450° C. for an hour. During the heat treatment,the oxide semiconductor film 106 is not exposed to the air to preventthe entry of water and hydrogen.

Note that a heat treatment apparatus is not limited to an electricfurnace, and may include a device for heating an object to be processedby heat conduction or heat radiation from a medium such as a heated gas.For example, a rapid thermal anneal (RTA) apparatus such as a lamp rapidthermal anneal (LRTA) apparatus or a gas rapid thermal anneal (GRTA)apparatus can be used. An LRTA apparatus is an apparatus for heating anobject to be processed by radiation of light (electromagnetic waves)emitted from a lamp such as a halogen lamp, a metal halide lamp, a xenonarc lamp, a carbon arc lamp, a high pressure sodium lamp, or a highpressure mercury lamp. A GRTA apparatus is an apparatus for heattreatment using a high temperature gas. As the high temperature gas,used is an inert gas which does not react with an object to be processedin heat treatment, such as nitrogen or a rare gas like argon.

For example, as the heat treatment, GRTA treatment may be performed asfollows. The object is put in an inert gas atmosphere that has beenheated, heated for several minutes, and then taken out of the inert gasatmosphere. GRTA treatment enables high-temperature heat treatment in ashort time. Moreover, GRTA treatment can be employed even when thetemperature exceeds the upper temperature limit of the object. Note thatthe inert gas may be switched to a gas containing oxygen during thetreatment. This is because defect levels in an energy gap due to oxygenvacancy can be reduced by performing the heat treatment in an atmospherecontaining oxygen.

Note that as the inert gas atmosphere, an atmosphere that containsnitrogen or a rare gas (e.g., helium, neon, or argon) as its mainconstituent and does not contain water, hydrogen, and the like isdesirably used. For example, the purity of nitrogen or a rare gas suchas helium, neon, or argon introduced into a heat treatment apparatus is6N (99.9999%) or higher, preferably 7N (99.99999%) or higher (that is,the impurity concentration is 1 ppm or lower, preferably 0.1 ppm orlower).

In any case, the i-type (intrinsic) or substantially i-type oxidesemiconductor film in which impurities are reduced by the heat treatmentis formed, whereby a transistor having extremely excellentcharacteristics can be realized.

The above heat treatment can be referred to as dehydration treatment,dehydrogenation treatment, or the like because of its advantageouseffect of removing hydrogen, water, and the like. The dehydrationtreatment or dehydrogenation treatment may be performed at the timing,for example, before the oxide semiconductor film is processed to have anisland shape. Such dehydration treatment or dehydrogenation treatmentmay be conducted once or plural times.

Next, the oxide semiconductor film 108 is subjected to treatment withoxygen 180 (also referred to as oxygen doping treatment or oxygen plasmadoping treatment) (see FIG. 2E). Here, the oxygen 180 contains at leastany of an oxygen radical, an oxygen atom, and an oxygen ion. Byperforming oxygen doping treatment on the oxide semiconductor film 108,the oxygen can be contained either or both in the oxide semiconductorfilm 108 or/and in the vicinity of the interface of the oxidesemiconductor film 108. In that case, the oxygen content is greater thanthe stoichiometric proportion of the oxide semiconductor film 108,preferably greater than the stoichiometric proportion and less thantwice the stoichiometric proportion. Alternatively, the oxygen contentmay be greater than Y, preferably greater than Y and less than 2Y, wherethe oxygen amount in the case where a material of the oxidesemiconductor film is single-crystalline is Y. Still alternatively, theoxygen content may be greater than Z, preferably greater than Z and lessthan 2Z based on the oxygen amount Z of the oxide semiconductor film inthe case where oxygen doping treatment is not performed. The reason whythe above preferable range has the upper limit is because the oxidesemiconductor film 108 might taken in hydrogen like a hydrogen-storingalloy when the oxygen content is too high. Note that in the oxidesemiconductor film, the oxygen content is higher than the hydrogencontent.

In the case of a material whose crystalline structure is expressed byInGaO₃(ZnO)_(m) (m>0), x in InGaZnO_(x) can be greater than 4 and lessthan 8 when the crystalline structure where m is 1 (InGaZnO₄) is used asthe reference, and x in InGaZn₂O_(x) can be greater than 5 and less than10 when the crystalline structure where m is 2 (InGaZn₂O₅) is used asthe reference. Such an excessive oxygen region may exist in part of theoxide semiconductor (including the interface).

In the oxide semiconductor film, oxygen is one of the main constituents.Thus, it is difficult to accurately estimate the oxygen concentration ofthe oxide semiconductor film by a method such as secondary ion massspectrometry (SIMS). In other words, it can be said that it is hard todetermine whether oxygen is intentionally added to the oxidesemiconductor film.

Incidentally, it is known that oxygen contains isotopes such as ¹⁷O and¹⁸O and the proportions of ¹⁷O and ¹⁸O in all of the oxygen atoms innature is about 0.037% and about 0.204%, respectively. That is to say,it is possible to measure the concentrations of these isotopes in theoxide semiconductor film by a method such as SIMS; therefore, the oxygenconcentration of the oxide semiconductor film may be able to beestimated more accurately by measuring the concentrations of theseisotopes. Thus, the concentrations of these isotopes may be measured todetermine whether oxygen is intentionally added to the oxidesemiconductor film.

For example, when the concentration of ¹⁸O is used as the reference, itcan be said that D1 (¹⁸O)>D2 (¹⁸O) is satisfied between theconcentration of an isotope of oxygen D1 (¹⁸O) in a region of the oxidesemiconductor film, which has been doped with oxygen, and theconcentration of an isotope of oxygen D2 (¹⁸O) in a region of the oxidesemiconductor film, which is not been doped with oxygen.

It is preferable that at least part of the oxygen 180 added to the oxidesemiconductor film have dangling bonds in the oxide semiconductor film.This is because such dangling bonds are linked with hydrogen remainingin the film so that hydrogen can be fixed (made to be immobile ions).

The oxygen 180 can be generated by a plasma generating apparatus or anozone generating apparatus. More specifically, when an apparatus foretching of a semiconductor device, an apparatus for ashing of a resistmask, or the like is used and the oxygen 180 is generated, the oxidesemiconductor film 108 can be processed.

Note that it is desirable to apply an electrical bias to the substratein order to perform oxygen doping more favorably.

Note that heat treatment (at a temperature of 150° C. to 470° C.) may beperformed on the oxide semiconductor film 108 which has been subjectedto the oxygen doping treatment. Through the heat treatment, water, ahydroxide, and the like generated by reaction between hydrogen andeither or both oxygen or/and the oxide semiconductor material can beremoved from the oxide semiconductor film. The heat treatment may beperformed in an atmosphere of nitrogen, oxygen, an ultra-dry air (an airwhere the moisture content is 20 ppm (−55° C. by conversion into a dewpoint) or less, preferably 1 ppm or less, further preferably 10 ppb orless when measurement is performed using a dew-point instrument of acavity ring down laser spectroscopy (CRDS) system), a rare gas (e.g.,argon or helium), or the like in which moisture, hydrogen, and the likeare sufficiently reduced. Further, the oxygen doping treatment and theheat treatment may be repeated. By repeatedly performing the oxygendoping treatment and the heat treatment, the transistor can have higherreliability. The number of repetitions can be set appropriately.

Then, the gate insulating film 110 is formed in contact with part of theoxide semiconductor film 108 so as to cover the source electrode 104 aand the drain electrode 104 b (see FIG. 2F).

The gate insulating film 110 can be formed in a manner similar to thatof the insulating film 102. That is, the gate insulating film 110 may beformed using a silicon oxide, a silicon nitride, an aluminum oxide, analuminum nitride, a gallium oxide, a mixed material thereof, or thelike. Note that a material having a high dielectric constant, such as ahafnium oxide, a tantalum oxide, an yttrium oxide, a hafnium silicate(HfSi_(x)O_(y) (x>0, y>0)), a hafnium silicate (HfSi_(x)O_(y) (x>0,y>0)) to which nitrogen is added, or a hafnium aluminate (HfAl_(x)O_(y)(x>0, y>0)) to which nitrogen is added may be used for the gateinsulating film 110 considering the function of the gate insulating filmof the transistor.

As in the case of the insulating film 102, a stacked structure may beemployed. In that case, it is further preferable to employ a stackedstructure of a film formed using an insulating material containing aconstituent similar to that of the oxide semiconductor film (hereinafterreferred to as a film a) and a film containing a material different fromthat of a constituent material of the film a (hereinafter referred to asa film b). The reason is as follows. When the gate insulating film 110has such a structure in which the film a and the film b are sequentiallystacked on the oxide semiconductor film side, charge is trappedpreferentially in a charge trapping center at the interface between thefilm a and the film b (compared with the interface between the oxidesemiconductor film and the film a). Thus, trapping of charge at theinterface of the oxide semiconductor film can be sufficientlysuppressed, resulting in higher reliability of the semiconductor device.

Note that as such a stacked structure, a stack of a gallium oxide filmand a silicon oxide film, a stack of a gallium oxide film and a siliconnitride film, or the like may be used.

Heat treatment is desirably performed after formation of the gateinsulating film 110. The heat treatment is performed at a temperature ofhigher than or equal to 250° C. and lower than or equal to 700° C.,preferably higher than or equal to 450° C. and lower than or equal to600° C. Note that the temperature of the heat treatment is preferablylower than the strain point of the substrate.

The heat treatment may be performed in an atmosphere of nitrogen,oxygen, ultra-dry air (air in which a water content is 20 ppm or less,preferably 1 ppm or less, further preferably 10 ppb or less), or a raregas (argon, helium, or the like). Note that it is preferable that water,hydrogen, and the like be not contained in the atmosphere of nitrogen,oxygen, ultra-dry air, or a rare gas. Further, the purity of nitrogen,oxygen, or a rare gas introduced into a heat treatment apparatus ispreferably 6N (99.9999%) or higher (that is, the impurity concentrationis 1 ppm or lower), further preferably 7N (99.99999%) or higher (thatis, the impurity concentration is 0.1 ppm or lower).

The heat treatment in this embodiment is performed while the oxidesemiconductor film 108 and the gate insulating film 110 are in contactwith each other. Thus, oxygen which may be reduced due to thedehydration (or dehydrogenation) treatment can be supplied to the oxidesemiconductor film 108. In this sense, the heat treatment can also bereferred to as supply of oxygen.

Note that there is no particular limitation on the timing of the heattreatment for supply of oxygen as long as it is after formation of theoxide semiconductor film 108. For example, the heat treatment for supplyof oxygen may be performed after the gate electrode is formed.Alternatively, the heat treatment for supply of oxygen may be performedfollowing the heat treatment for dehydration or the like, the treatmentfor dehydration or the like may also serve as the heat treatment forsupply of oxygen, or the treatment for supply of oxygen may also serveas the heat treatment for dehydration or the like.

As described above, the heat treatment for dehydration or the like andoxygen doping treatment or the heat treatment for supply of oxygen areapplied, whereby the oxide semiconductor film 108 can be highly purifiedso as to contain impurities as little as possible. The highly-purifiedoxide semiconductor film 108 contains extremely few (close to zero)carriers derived from a donor.

Then, the gate electrode 112 is formed (see FIG. 2G). The gate electrode112 can be formed using a metal material such as molybdenum, titanium,tantalum, tungsten, aluminum, copper, neodymium, or scandium or an alloymaterial which contains any of these materials as its main component.Note that the gate electrode 112 may have a single-layer structure or astacked structure.

Note that an insulating film may be formed after formation of the gateelectrode 112. The insulating film may be formed using a silicon oxide,a silicon nitride, an aluminum oxide, an aluminum nitride, a galliumoxide, a mixed material thereof, or the like. In particular, a siliconnitride film is preferable as the insulating film because doped oxygencan be prevented from being released to the outside and entry ofhydrogen and the like to the oxide semiconductor film 108 from theoutside can be suppressed effectively. A wiring connected to the sourceelectrode 104 a, the drain electrode 104 b, the gate electrode 112, orthe like may be formed.

Through the above process, the transistor 120 is formed.

The example is described above in which the oxide semiconductor film 108that has been processed to have an island shape and highly purified issubjected to oxygen doping treatment; however, one embodiment of thedisclosed invention is not limited to this. For example, the oxidesemiconductor film may be processed to have an island shape after highpurification and oxygen doping treatment are performed, or oxygen dopingtreatment may be performed after formation of the source electrode 104 aand the drain electrode 104 b.

<Modified Examples of Semiconductor Device>

FIGS. 3A to 3D are cross-sectional views of a transistor 130, atransistor 140, a transistor 150, and a transistor 160 as modifiedexamples of the transistor 120 in FIGS. 1A to 1C.

The transistor 130 in FIG. 3A is the same as the transistor 120 in thatit includes the insulating film 102, the source electrode 104 a, thedrain electrode 104 b, the oxide semiconductor film 108, the gateinsulating film 110, and the gate electrode 112. The difference betweenthe transistor 130 and the transistor 120 is the presence of theinsulating film 114 covering the above components. That is, thetransistor 130 includes the insulating film 114. The other componentsare the same as those of the transistor 120 in FIGS. 1A to 1C; thus, thedescription on FIGS. 1A to 1C can be referred to for the details.

The transistor 140 in FIG. 3B is the same as the transistor 120 in FIGS.1A to 1C in that it includes the above components. The differencebetween the transistor 140 and the transistor 120 is the stackingsequence of the source electrode 104 a and the drain electrode 104 b,and the oxide semiconductor film 108. That is, in the transistor 120,the source electrode 104 a and the drain electrode 104 b are formedbefore formation of the oxide semiconductor film 108, whereas in thetransistor 140, the oxide semiconductor film 108 is formed beforeformation of the source electrode 104 a and the drain electrode 104 b.The other components are the same as those in FIGS. 1A to 1C. Note thatthe transistor 140 may include the insulating film 114 like thetransistor 130.

The transistor 150 in FIG. 3C is the same as the transistor 120 in FIGS.1A to 1C in that it includes the above components. The differencebetween the transistor 150 and the transistor 120 is the insulating filmon the substrate 100 side. In other words, the transistor 150 includes astack of an insulating film 102 a and an insulating film 102 b. Theother components are the same as those in FIG. 1B.

When the stack of the insulating film 102 a and the insulating film 102b is provided in this manner, charge is trapped preferentially in acharge trapping center at the interface between the insulating film 102a and the insulating film 102 b. Thus, trapping of charge at theinterface of the oxide semiconductor film 108 can be sufficientlysuppressed, resulting in higher reliability of a semiconductor device.

Note that it is desirable to form the insulating film 102 b with the useof an insulating material containing a constituent similar to that ofthe oxide semiconductor film 108 and to form the insulating film 102 acontaining a material different from a constituent material of theinsulating film 102 b. For example, in the case where the oxidesemiconductor film 108 is formed using an In—Ga—Zn—O-based oxidesemiconductor material, a gallium oxide or the like is given as such aninsulating material containing a constituent similar to that of theoxide semiconductor film 108. In this case, a stack of a gallium oxidefilm and a silicon oxide film, a stack of a gallium oxide film and asilicon nitride film, or the like may be used.

The transistor 160 in FIG. 3D is the same as the transistor 120 in FIGS.1A to 1C in that it includes the above components. The differencesbetween the transistor 160 and the transistor 120 are the insulatingfilm and the gate insulating film on the substrate 100 side. In otherwords, the transistor 160 includes a stack of the insulating film 102 aand the insulating film 102 b and a stack of a gate insulating film 110a and a gate insulating film 110 b. The other components are the same asthose in FIGS. 1A to 1C.

When the stack of the insulating film 102 a and the insulating film 102b and the stack of the gate insulating film 110 a and the gateinsulating film 110 b are provided, charge is trapped preferentially atthe interface between the insulating film 102 a and the insulating film102 b and the interface between the gate insulating film 110 a and thegate insulating film 110 b. Thus, trapping of charge at the interface ofthe oxide semiconductor film 108 can be sufficiently suppressed,resulting in higher reliability of the semiconductor device.

Note that it is desirable that each of the insulating film 102 b and thegate insulating film 110 a (namely, the insulating films in contact withthe oxide semiconductor film 108) be formed with the use of aninsulating material containing a constituent similar to that of theoxide semiconductor film 108, and the insulating film 102 a and the gateinsulating film 110 b contain materials different from constituentmaterials of the insulating film 102 b and the gate insulating film 110a, respectively. For example, in the case where the oxide semiconductorfilm 108 is formed using an In—Ga—Zn—O-based oxide semiconductormaterial, a gallium oxide or the like is given as such an insulatingmaterial containing a constituent similar to that of the oxidesemiconductor film 108. In this case, a stack of a gallium oxide filmand a silicon oxide film, a stack of a gallium oxide film and a siliconnitride film, or the like may be used.

The transistor according to this embodiment includes an oxidesemiconductor film highly purified to be electrically i-type (intrinsic)by removing impurities such as hydrogen, water, a hydroxyl group, andhydride (also referred to as a hydrogen compound) from the oxidesemiconductor and supplying oxygen which might be reduced in a step ofremoving impurities, through heat treatment. The transistor includingthe oxide semiconductor film highly purified in such a manner haselectrical characteristics such as the threshold voltage, which are lesslikely to change, and thus is electrically stable.

In particular, when the oxygen content in the oxide semiconductor filmis increased by oxygen doping treatment, deterioration due to electricalbias stress or heat stress can be suppressed and deterioration due tolight can be reduced.

As described above, according to one embodiment of the disclosedinvention, a highly reliable transistor can be provided.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

Embodiment 2

In this embodiment, another example of a manufacturing method of asemiconductor device will be described with reference to FIGS. 4A to 4Fand FIGS. 5A to 5C.

<Structural Example of Semiconductor Device>

The structure of a semiconductor device manufactured by themanufacturing method according to this embodiment is similar to that ofthe transistor 120 of the above embodiment. That is, the semiconductordevice includes, over the substrate 100, the insulating film 102, thesource electrode 104 a, the drain electrode 104 b, the oxidesemiconductor film 108, the gate insulating film 110, and the gateelectrode 112 (see FIGS. 1A to 1C).

As described in the above embodiment, in the transistor 120, the oxidesemiconductor film 108 has been subjected to oxygen doping treatment. Inthis embodiment, the insulating film 102 and the gate insulating film110 have also been subjected to oxygen doping treatment. By such oxygendoping treatment, the transistor 120 can have higher reliability. As inthe above embodiment, transistors having modified structures can also beformed (see FIGS. 3A to 3D).

<Example of Manufacturing Process of Semiconductor Device>

An example of a manufacturing process of the semiconductor device willbe described below with reference to FIGS. 4A to 4F and FIGS. 5A to 5C.

First, the insulating film 102 is formed over the substrate 100 (seeFIG. 4A).

There is no particular limitation on the property of a material and thelike of the substrate 100 as long as the material has heat resistancehigh enough to withstand at least heat treatment performed later. Forexample, a glass substrate, a ceramic substrate, a quartz substrate, ora sapphire substrate can be used as the substrate 100. Alternatively, asingle crystal semiconductor substrate or a polycrystallinesemiconductor substrate made of silicon, silicon carbide, or the like, acompound semiconductor substrate made of silicon germanium or the like,an SOI substrate, or the like may be used as the substrate 100. Stillalternatively, any of these substrates further provided with asemiconductor element may be used as the substrate 100.

A flexible substrate may alternatively be used as the substrate 100.When a transistor is provided over the flexible substrate, thetransistor may be formed directly on the flexible substrate, or thetransistor may be formed over a different substrate and then separatedto be transferred to the flexible substrate. In order to separate thetransistor to transfer it to the flexible substrate, a separation layeris preferably formed between the different substrate and the transistor.

The insulating film 102 serves as a base. Specifically, the insulatingfilm 102 may be formed using a silicon oxide, a silicon nitride, analuminum oxide, an aluminum nitride, a gallium oxide, a mixed materialthereof, or the like. The insulating film 102 may have a single-layerstructure or a stacked structure using an insulating film including anyof the above materials.

There is no particular limitation on the method for forming theinsulating film 102. For example, the insulating film 102 may be formedby a deposition method such as a plasma CVD method or a sputteringmethod. A sputtering method is preferable in terms of low possibility ofentry of hydrogen, water, and the like.

Note that it is particularly preferable to form the insulating film 102with the use of an insulating material containing a constituent similarto that of an oxide semiconductor film formed later. Such a material iscompatible with an oxide semiconductor film; thus, when it is used forthe insulating film 102, the state of the interface with the oxidesemiconductor film can be kept favorably. Here, “a constituent similarto that of an oxide semiconductor film” means one or more of elementsselected from constituent elements of the oxide semiconductor film. Forexample, in the case where the oxide semiconductor film is formed usingan In—Ga—Zn—O-based oxide semiconductor material, a gallium oxide or thelike is given as such an insulating material containing a constituentsimilar to that of the oxide semiconductor film.

In the case where the insulating film 102 has a stacked structure, it isfurther preferable to employ a stacked structure of a film formed usingan insulating material containing a constituent similar to that of theoxide semiconductor film (hereinafter referred to as a film a) and afilm containing a material different from that of a constituent materialof the film a (hereinafter referred to as a film b). The reason is asfollows. When the insulating film 102 has such a structure in which thefilm a and the film b are sequentially stacked on the oxidesemiconductor film side, charge is trapped preferentially in a chargetrapping center at the interface between the film a and the film b(compared with the interface between the oxide semiconductor film andthe film a). Thus, trapping of charge at the interface of the oxidesemiconductor film can be sufficiently suppressed, resulting in higherreliability of the semiconductor device.

Note that as such a stacked structure, a stack of a gallium oxide filmand a silicon oxide film, a stack of a gallium oxide film and a siliconnitride film, or the like may be used.

Next, the insulating film 102 is subjected to treatment with oxygen 180a (also referred to as oxygen doping treatment or oxygen plasma doping)(see FIG. 4B). The oxygen 180 a contains at least any of an oxygenradical, an oxygen atom, and an oxygen ion. By performing oxygen dopingtreatment on the insulating film 102, the oxygen can be contained in theinsulating film 102 and either or both in the oxide semiconductor film108 formed later or/and in the vicinity of the interface of the oxidesemiconductor film 108. In that case, the oxygen content is greater thanthe stoichiometric proportion of the insulating film 102, preferablygreater than the stoichiometric proportion and less than four times thestoichiometric proportion, further preferably greater than thestoichiometric proportion and less than twice the stoichiometricproportion. Alternatively, the oxygen content may be greater than Y,preferably greater than Y and less than 4Y, where the oxygen amount inthe case where a material of the insulating film is single-crystallineis Y. Still alternatively, the oxygen content may be greater than Z,preferably greater than Z and less than 4Z based on the oxygen amount Zof the insulating film in the case where oxygen doping treatment is notperformed.

In the case of using a gallium oxide whose composition is expressed byGaO_(x) (x>0), a single crystal gallium oxide is Ga₂O₃; therefore, x canbe greater than 1.5 and less than 6 (i.e., the amount of O is greaterthan 1.5 times and less than 6 times that of Ga). Alternatively, in thecase of using a silicon oxide whose composition is expressed by SiO_(x)(x>0), when the silicon oxide is SiO₂ (i.e., the amount of O is twicethat of Si), x can be greater than 2 and less than 8 (i.e., the amountof O is greater than twice and less than 8 times that of Si). Such anexcessive oxygen region may exist in part of the insulating film(including the interface).

It is preferable that at least part of the oxygen 180 a added to theinsulating film have dangling bonds in the oxide semiconductor filmafter being supplied to the oxide semiconductor. This is because suchdangling bonds are linked with hydrogen remaining in the film so thathydrogen can be fixed (made to be immobile ions).

The oxygen 180 a may be generated by a plasma generating apparatus or anozone generating apparatus. More specifically, when an apparatus foretching of a semiconductor device, an apparatus for ashing of a resistmask, or the like is used and the oxygen 180 a is generated, theinsulating film 102 can be processed.

Note that it is desirable to apply an electrical bias to the substratein order to perform oxygen doping more favorably.

Next, a conductive film for forming the source electrode and the drainelectrode (including a wiring formed in the same layer as the sourceelectrode and the drain electrode) is formed over the insulating film102 and processed to form the source electrode 104 a and the drainelectrode 104 b (see FIG. 4C). The channel length L of the transistor isdetermined by the distance between the edges of the source electrode 104a and the drain electrode 104 b which are formed here.

Examples of the conductive film used for the source electrode 104 a andthe drain electrode 104 b are a metal film containing an elementselected from Al, Cr, Cu, Ta, Ti, Mo, and W, and a metal nitride filmcontaining any of the above elements as its constituent (e.g., atitanium nitride film, a molybdenum nitride film, and a tungsten nitridefilm). Alternatively, a conductive film may be used in which ahigh-melting-point metal film of Ti, Mo, W, or the like or a metalnitride film of any of these elements (a titanium nitride film, amolybdenum nitride film, or a tungsten nitride film) may be stacked onone of or both a bottom side and a top side of a metal film of Al, Cu,or the like.

Alternatively, the conductive film used for the source electrode 104 aand the drain electrode 104 b may be formed using a conductive metaloxide. As the conductive metal oxide, an indium oxide (In₂O₃), a tinoxide (SnO₂), a zinc oxide (ZnO), an indium oxide-tin oxide alloy(In₂O₃—SnO₂, which is abbreviated to ITO), an indium oxide-zinc oxidealloy (In₂O₃—ZnO), or any of these metal oxide materials containing asilicon oxide may be used.

The conductive film may be processed by etching with the use of a resistmask. Ultraviolet, a KrF laser light, an ArF laser light, or the like ispreferably used for light exposure for forming a resist mask for theetching.

In the case where the channel length L is less than 25 nm, the lightexposure at the time of forming the resist mask is preferably performedusing, for example, extreme ultraviolet having an extremely shortwavelength of several nanometers to several tens of nanometers. In thelight exposure using extreme ultraviolet, the resolution is high and thefocus depth is large. Thus, the channel length L of the transistorformed later can be reduced, whereby the operation speed of a circuitcan be increased.

An etching step may be performed with the use of a resist mask formedusing a so-called multi-tone mask. A resist mask formed using amulti-tone mask has a plurality of thicknesses and can be furtherchanged in shape by ashing; thus, such a resist mask can be used in aplurality of etching steps for different patterns. Therefore, a resistmask for at least two kinds of patterns can be formed using a multi-tonemask, resulting in simplification of the process.

Next, an oxide semiconductor film is formed over the insulating film 102and in contact with the source electrode 104 a and the drain electrode104 b and then is processed to form an oxide semiconductor film 106having an island shape (see FIG. 4D).

The oxide semiconductor film is desirably formed by a method by whichhydrogen, water, and the like do not easily enter the film, such as asputtering method. The thickness of the oxide semiconductor film isdesirably larger than or equal to 3 nm and smaller than or equal to 30nm. This is because the transistor might possibly be normally on whenthe oxide semiconductor film is too thick (e.g., the thickness is 50 nmor more).

As a material of the oxide semiconductor film, any of the followingmaterials can be used: a four-component metal oxide such as anIn—Sn—Ga—Zn—O-based material; three-component metal oxides such as anIn—Ga—Zn—O-based material, an In—Sn—Zn—O-based material, anIn—Al—Zn—O-based material, a Sn—Ga—Zn—O-based material, anAl—Ga—Zn—O-based material, and a Sn—Al—Zn—O-based material;two-component metal oxides such as an In—Zn—O-based material, aSn—Zn—O-based material, an Al—Zn—O-based material, a Zn—Mg—O-basedmaterial, a Sn—Mg—O-based material, an In—Mg—O-based material, and anIn—Ga—O-based material; and single-component metal oxides such as anIn—O-based material, a Sn—O-based material, and a Zn—O-based material.In addition, the above materials may contain silicon oxide. Here, forexample, an In—Ga—Zn—O-based material means an oxide film containingindium (In), gallium (Ga), and zinc (Zn), and there is no particularlimitation on the composition ratio thereof. Further, theIn—Ga—Zn—O-based material may contain another element in addition to In,Ga, and Zn.

The oxide semiconductor film may be a thin film formed using a materialexpressed by the chemical formula, InMO₃(ZnO)_(m) (m>0). Here, Mrepresents one or more metal elements selected from Ga, Al, Mn, and Co.For example, M may be Ga, Ga and Al, Ga and Mn, Ga and Co, or the like.

In the case where an In—Zn—O-based material is used for the oxidesemiconductor film, a target with the following composition ratio isused: the composition ratio of In:Zn is 50:1 to 1:2 in an atomic ratio(In₂O₃:ZnO=25:1 to 1:4 in a molar ratio), preferably 20:1 to 1:1 in anatomic ratio (In₂O₃:ZnO=10:1 to 1:2 in a molar ratio), furtherpreferably 15:1 to 1.5:1 in an atomic ratio (In₂O₃:ZnO=15:2 to 3:4 in amolar ratio. For example, a target used for the formation of anIn—Zn—O-based oxide semiconductor has the following atomic ratio: theatomic ratio of In:Zn:O is X:Y:Z, where Z>1.5X+Y.

In this embodiment, the oxide semiconductor film is formed by asputtering method using an In—Ga—Zn—O-based oxide semiconductordeposition target.

As the In—Ga—Zn—O-based oxide semiconductor deposition target, forexample, an oxide semiconductor deposition target with the followingcomposition ratio may be used: In₂O₃:Ga₂O₃:ZnO=1:1:1 [molar ratio]. Notethat it is not necessary to limit the material and the composition ratioof the target to the above. For example, an oxide semiconductordeposition target with the following composition ratio may alternativelybe used: In₂O₃:Ga₂O₃:ZnO=1:1:2 [molar ratio].

The fill rate of the oxide semiconductor deposition target is higherthan or equal to 90% and lower than or equal to 100%, preferably, higherthan or equal to 95% and lower than or equal to 99.9%. With the use ofthe oxide semiconductor deposition target with high fill rate, a denseoxide semiconductor film can be formed.

The deposition atmosphere may be a rare gas (typically argon)atmosphere, an oxygen atmosphere, or a mixed atmosphere containing arare gas and oxygen. Moreover, it is desirably an atmosphere using ahigh-purity gas in which impurities containing hydrogen atoms, such ashydrogen, water, a hydroxyl group, and hydride, are removed becauseentry of hydrogen, water, a hydroxyl group, and hydride into the oxidesemiconductor film can be prevented.

In forming the oxide semiconductor film, oxygen in the insulating film102 is supplied to the oxide semiconductor film in some cases. When theinsulating film 102 is thus doped with oxygen, it is possible to formthe oxide semiconductor film sufficiently doped with oxygen.

More specifically, for example, the oxide semiconductor film can beformed as follows.

First, the substrate 100 is placed in a deposition chamber kept underreduced pressure, and the substrate temperature is set to a temperaturehigher than or equal to 100° C. and lower than or equal to 600° C.,preferably higher than or equal to 200° C. and lower than or equal to400° C. This is because the concentration of an impurity contained inthe oxide semiconductor film can be reduced when deposition is performedwhile the substrate 100 is heated. This is also because damage to theoxide semiconductor film due to sputtering can be reduced.

Then, a high-purity gas in which impurities containing hydrogen atoms,such as hydrogen and moisture, are sufficiently removed is introducedinto the deposition chamber from which remaining moisture is beingremoved, and the oxide semiconductor film is formed over the substrate100 with the use of the target. To remove moisture remaining in thedeposition chamber, an entrapment vacuum pump such as a cryopump, an ionpump, or a titanium sublimation pump is desirably used an evacuationmeans. Further, an evacuation means may be a turbo molecular pumpprovided with a cold trap. In the deposition chamber which is evacuatedwith the cryopump, a hydrogen molecule, a compound containing a hydrogenatom, such as water (H₂O), (further preferably, also a compoundcontaining a carbon atom), and the like are removed, whereby theconcentration of an impurity in the oxide semiconductor film formed inthe deposition chamber can be reduced.

An example of the deposition condition is as follows: the distancebetween the substrate and the target is 100 mm, the pressure is 0.6 Pa,the direct-current (DC) power is 0.5 kW, and the deposition atmosphereis an oxygen atmosphere (the flow rate of the oxygen is 100%). Note thata pulse direct current power source is preferable because generation ofpowdery substances (also referred to as particles or dust) in depositioncan be reduced and unevenness in film thickness can be reduced.

The oxide semiconductor film can be processed by being etched after amask having a desired shape is formed over the oxide semiconductor film.The mask may be formed by a method such as photolithography or an inkjet method.

For the etching of the oxide semiconductor film, either wet etching ordry etching may be employed. It is needless to say that both of them maybe employed in combination.

After that, heat treatment is performed on the oxide semiconductor film106 so that the highly-purified oxide semiconductor film 108 is formed(see FIG. 4E). Hydrogen (including water and a hydroxyl group) in theoxide semiconductor film 106 is removed through the heat treatment andthe structure of the oxide semiconductor film is modified, so thatdefect levels in an energy gap can be reduced. Further, through thisheat treatment, oxygen in the insulating film 102 is supplied to theoxide semiconductor film in some cases. The heat treatment is performedat a temperature of higher than or equal to 250° C. and lower than orequal to 650° C., preferably higher than or equal to 450° C. and lowerthan or equal to 600° C. The temperature of the heat treatment ispreferably lower than the strain point of the substrate.

The heat treatment may be performed, for example, in such a manner thatan object to be processed is introduced into an electric furnace inwhich a resistance heating element or the like is used and heated in anitrogen atmosphere at 450° C. for an hour. During the heat treatment,the oxide semiconductor film 106 is not exposed to the air to preventthe entry of water and hydrogen.

Note that a heat treatment apparatus is not limited to an electricfurnace, and may include a device for heating an object to be processedby heat conduction or heat radiation from a medium such as a heated gas.For example, a rapid thermal anneal (RTA) apparatus such as a lamp rapidthermal anneal (LRTA) apparatus or a gas rapid thermal anneal (GRTA)apparatus can be used. An LRTA apparatus is an apparatus for heating anobject to be processed by radiation of light (electromagnetic waves)emitted from a lamp such as a halogen lamp, a metal halide lamp, a xenonarc lamp, a carbon arc lamp, a high pressure sodium lamp, or a highpressure mercury lamp. A GRTA apparatus is an apparatus for heattreatment using a high temperature gas. As the high temperature gas,used is an inert gas which does not react with an object to be processedin heat treatment, such as nitrogen or a rare gas like argon.

For example, as the heat treatment, GRTA treatment may be performed asfollows. The object is put in an inert gas atmosphere that has beenheated, heated for several minutes, and then taken out of the inert gasatmosphere. GRTA treatment enables high-temperature heat treatment in ashort time. Moreover, GRTA treatment can be employed even when thetemperature exceeds the upper temperature limit of the object. Note thatthe inert gas may be switched to a gas containing oxygen during thetreatment. This is because defect levels in an energy gap due to oxygenvacancy can be reduced by performing the heat treatment in an atmospherecontaining oxygen.

Note that as the inert gas atmosphere, an atmosphere that containsnitrogen or a rare gas (e.g., helium, neon, or argon) as its mainconstituent and does not contain water, hydrogen, and the like isdesirably used. For example, the purity of nitrogen or a rare gas suchas helium, neon, or argon introduced into a heat treatment apparatus is6N (99.9999%) or higher, preferably 7N (99.99999%) or higher (that is,the impurity concentration is 1 ppm or lower, preferably 0.1 ppm orlower).

In any case, the i-type (intrinsic) or substantially i-type oxidesemiconductor film in which impurities are reduced by the heat treatmentis formed, whereby a transistor having extremely excellentcharacteristics can be realized.

The above heat treatment can be referred to as dehydration treatment,dehydrogenation treatment, or the like because of its advantageouseffect of removing hydrogen, water, and the like. The dehydrationtreatment or dehydrogenation treatment may be performed at the timing,for example, before the oxide semiconductor film is processed to have anisland shape. Such dehydration treatment or dehydrogenation treatmentmay be conducted once or plural times.

Next, the oxide semiconductor film 108 is subjected to treatment withoxygen 180 b (see FIG. 4F). The oxygen 180 b contains at least any of anoxygen radical, an oxygen atom, and an oxygen ion. By performing oxygendoping treatment on the oxide semiconductor film 108, the oxygen can becontained either or both in the oxide semiconductor film 108 or/and inthe vicinity of the interface of the oxide semiconductor film 108. Inthat case, the oxygen content is greater than the stoichiometricproportion of the oxide semiconductor film 108, preferably greater thanthe stoichiometric proportion and less than twice the stoichiometricproportion. Alternatively, the oxygen content may be greater than Y,preferably greater than Y and less than 2Y, where the oxygen amount inthe case where a material of the oxide semiconductor film issingle-crystalline is Y. Still alternatively, the oxygen content may begreater than Z, preferably greater than Z and less than 2Z based on theoxygen amount Z of the oxide semiconductor film in the case where oxygendoping treatment is not performed. The reason why the above preferablerange has the upper limit is because the oxide semiconductor film 108might taken in hydrogen like a hydrogen-storing alloy when the oxygencontent is too high.

In the case of a material whose crystalline structure is expressed byInGaO₃(ZnO)_(m) (m>0), x in InGaZnO_(x) can be greater than 4 and lessthan 8 when the crystalline structure where m is 1 (InGaZnO₄) is used asthe reference, and x in InGaZn₂O_(x) can be greater than 5 and less than10 when the crystalline structure where m is 2 (InGaZn₂O₅) is used asthe reference. Such an excessive oxygen region may exist in part of theoxide semiconductor film (including the interface).

It is preferable that at least part of the oxygen 180 b added to theoxide semiconductor film have dangling bonds in the oxide semiconductorfilm. This is because such dangling bonds are linked with hydrogenremaining in the film so that hydrogen can be fixed (made to be immobileions).

The oxygen 180 b can be generated by a plasma generating apparatus or anozone generating apparatus. More specifically, when an apparatus foretching of a semiconductor device, an apparatus for ashing of a resistmask, or the like is used and the oxygen 180 b is generated, the oxidesemiconductor film 108 can be processed.

Note that it is desirable to apply an electrical bias to the substratein order to perform oxygen doping more favorably.

Heat treatment (at a temperature of 150° C. to 470° C.) may be performedon the oxide semiconductor film 108 which has been subjected to theoxygen doping treatment. Through the heat treatment, water, a hydroxide,and the like generated by reaction between hydrogen and either/both ofoxygen or/and the material of the oxide semiconductor can be removedfrom the oxide semiconductor film. The heat treatment may be performedin an atmosphere of nitrogen, oxygen, an ultra-dry air (an air where themoisture content is 20 ppm or less, preferably 1 ppm or less, furtherpreferably 10 ppb or less), a rare gas (e.g., argon or helium), or thelike in which moisture, hydrogen, and the like are sufficiently reduced.Further, the oxygen doping treatment and the heat treatment may berepeated. By repeatedly performing the oxygen doping treatment and theheat treatment, the transistor can have higher reliability. The numberof repetitions can be set appropriately.

Then, the gate insulating film 110 is formed in contact with part of theoxide semiconductor film 108 so as to cover the source electrode 104 aand the drain electrode 104 b (see FIG. 5A).

The gate insulating film 110 can be formed in a manner similar to thatof the insulating film 102. That is, the gate insulating film 110 may beformed using a silicon oxide, a silicon nitride, an aluminum oxide, analuminum nitride, a gallium oxide, a mixed material thereof, or thelike. Note that a material having a high dielectric constant, such as ahafnium oxide, a tantalum oxide, an yttrium oxide, a hafnium silicate(HfSi_(x)O_(y) (x>0, y>0)), a hafnium silicate (HfSi_(x)O_(y) (x>0,y>0)) to which nitrogen is added, or a hafnium aluminate (HfSi_(x)O_(y)(x>0, y>0)) to which nitrogen is added may be used for the gateinsulating film 110 considering the function of the gate insulating filmof the transistor.

As in the case of the insulating film 102, a stacked structure may beemployed. In that case, it is further preferable to employ a stackedstructure of a film formed using an insulating material containing aconstituent similar to that of the oxide semiconductor film (hereinafterreferred to as a film a) and a film containing a material different fromthat of a constituent material of the film a (hereinafter referred to asa film b). The reason is as follows. When the gate insulating film 110has such a structure in which the film a and the film b are sequentiallystacked on the oxide semiconductor film side, charge is trappedpreferentially in a charge trapping center at the interface between thefilm a and the film b (compared with the interface between the oxidesemiconductor film and the film a). Thus, trapping of charge at theinterface of the oxide semiconductor film can be sufficientlysuppressed, resulting in higher reliability of the semiconductor device.

Note that as such a stacked structure, a stack of a gallium oxide filmand a silicon oxide film, a stack of a gallium oxide film and a siliconnitride film, or the like may be used.

Heat treatment is desirably performed after formation of the gateinsulating film 110. The heat treatment is performed at a temperature ofhigher than or equal to 250° C. and lower than or equal to 700° C.,preferably higher than or equal to 450° C. and lower than or equal to600° C. Note that the temperature of the heat treatment is preferablylower than the strain point of the substrate.

The heat treatment may be performed in an atmosphere of nitrogen,oxygen, ultra-dry air (air in which a water content is 20 ppm or less,preferably 1 ppm or less, further preferably 10 ppb or less), or a raregas (argon, helium, or the like). Note that it is preferable that water,hydrogen, and the like be not contained in the atmosphere of nitrogen,oxygen, ultra-dry air, or a rare gas. Further, the purity of nitrogen,oxygen, or a rare gas introduced into a heat treatment apparatus ispreferably 6N (99.9999%) or higher (that is, the impurity concentrationis 1 ppm or lower), further preferably 7N (99.99999%) or higher (thatis, the impurity concentration is 0.1 ppm or lower).

The heat treatment in this embodiment is performed while the oxidesemiconductor film 108 is in contact with the insulating film 102 andthe gate insulating film 110. Thus, oxygen which may be reduced due tothe dehydration (or dehydrogenation) treatment can be supplied to theoxide semiconductor film 108 from the insulating film 102 or the like.In this sense, the heat treatment can also be referred to as supply ofoxygen.

Note that there is no particular limitation on the timing of the heattreatment for supply of oxygen as long as it is after formation of theoxide semiconductor film 108. For example, the heat treatment for supplyof oxygen may be performed after the gate electrode is formed.Alternatively, the heat treatment for supply of oxygen may be performedfollowing the heat treatment for dehydration, the treatment fordehydration may also serve as the heat treatment for supply of oxygen,or the treatment for supply of oxygen may also serve as the heattreatment for dehydration.

As described above, the heat treatment for dehydration and oxygen dopingtreatment or the heat treatment for supply of oxygen are applied,whereby the oxide semiconductor film 108 can be highly purified so as tocontain impurities as little as possible. The highly-purified oxidesemiconductor film 108 contains extremely few (close to zero) carriersderived from a donor.

Next, the gate insulating film 110 is subjected to treatment with oxygen180 c (see FIG. 5B). The oxygen 180 c contains at least any of an oxygenradical, an oxygen atom, and an oxygen ion. By performing oxygen dopingtreatment on the gate insulating film 110, the oxygen can be containedin the gate insulating film 110 and either or both in the oxidesemiconductor film 108 or/and in the vicinity of the interface of theoxide semiconductor film 108. In that case, the oxygen content isgreater than the stoichiometric proportion of the gate insulating film110, preferably greater than the stoichiometric proportion and less thanfour times the stoichiometric proportion, further preferably greaterthan the stoichiometric proportion and less than twice thestoichiometric proportion. Alternatively, the oxygen content may begreater than Y, preferably greater than Y and less than 4Y, where theoxygen amount in the case where a material of the gate insulating filmis single-crystalline is Y. Still alternatively, the oxygen content maybe greater than Z, preferably greater than Z and less than 4Z based onthe oxygen amount Z of the gate insulating film in the case where oxygendoping treatment is not performed.

In the case of using a gallium oxide whose composition is expressed byGaO_(x) (x>0), a single crystal gallium oxide is Ga₂O₃, so that x can begreater than 1.5 and less than 6 (i.e., the amount of O is greater than1.5 times and less than 6 times that of Ga). Alternatively, in the caseof using a silicon oxide whose composition is expressed by SiO_(x)(x>0), when the silicon oxide is SiO₂ (i.e., the amount of O is twicethat of Si), x can be greater than 2 and less than 8 (i.e., the amountof O is greater than twice and less than 8 times that of Si). Such anexcessive oxygen region may exist in part of the insulating film(including the interface).

It is preferable that at least part of the oxygen 180 c added to theinsulating film have dangling bonds in the oxide semiconductor filmafter being supplied to the oxide semiconductor. This is because suchdangling bonds are linked with hydrogen remaining in the film so thathydrogen can be fixed (made to be immobile ions).

The oxygen 180 c may be generated by a plasma generating apparatus or anozone generating apparatus. More specifically, when an apparatus foretching of a semiconductor device, an apparatus for ashing of a resistmask, or the like is used and the oxygen 180 c is generated, the gateinsulating film 110 can be processed.

Note that it is desirable to apply an electrical bias to the substratein order to perform oxygen doping more favorably.

Note that heat treatment may be performed after the oxygen dopingtreatment. Through this heat treatment, a sufficient amount of oxygencan be supplied to the oxide semiconductor film. There is no limitationon the timing of heat treatment for achieving the effect as long as itis after the oxygen doping treatment. Further, the oxygen dopingtreatment and the heat treatment may be repeated. By repeatedlyperforming the oxygen doping treatment and the heat treatment, thetransistor can have higher reliability. The number of repetitions can beset appropriately.

Then, the gate electrode 112 is formed (see FIG. 5C). The gate electrode112 can be formed using a metal material such as molybdenum, titanium,chromium, tantalum, tungsten, aluminum, copper, neodymium, or scandiumor an alloy material which contains any of these materials as its maincomponent. Note that the gate electrode 112 may have a single-layerstructure or a stacked structure.

Note that an insulating film may be formed after formation of the gateelectrode 112. The insulating film may be formed using a silicon oxide,a silicon nitride, an aluminum oxide, an aluminum nitride, a galliumoxide, a mixed material thereof, or the like. In particular, a siliconnitride film is preferable as the insulating film because doped oxygencan be prevented from being released to the outside and entry ofhydrogen and the like to the oxide semiconductor film 108 from theoutside can be suppressed effectively. A wiring connected to the sourceelectrode 104 a, the drain electrode 104 b, the gate electrode 112, orthe like may be formed.

Through the above process, the transistor 120 is formed.

The example is described above in which oxygen doping treatment isperformed on all of the insulating film 102, the oxide semiconductorfilm 108, and the gate insulating film 110; however, one embodiment ofthe disclosed invention is not limited to this. For example, oxygendoping treatment may be performed on the insulating film 102 and theoxide semiconductor film 108 or the oxide semiconductor film 108 and thegate insulating film 110.

The transistor according to this embodiment includes an oxidesemiconductor film highly purified to be electrically i-type (intrinsic)by removing impurities such as hydrogen, water, a hydroxyl group, andhydride (also referred to as a hydrogen compound) from the oxidesemiconductor and supplying oxygen which might be reduced in a step ofremoving impurities, through heat treatment. The transistor includingthe oxide semiconductor film highly purified in such a manner haselectrical characteristics such as the threshold voltage, which are lesslikely to change, and thus is electrically stable.

In particular, when the oxygen content in the oxide semiconductor filmis increased by oxygen doping treatment, deterioration due to electricalbias stress or heat stress can be suppressed and deterioration due tolight can be reduced.

As described above, according to one embodiment of the disclosedinvention, a highly reliable transistor can be provided.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

Embodiment 3

In this embodiment, another example of a method for manufacturing asemiconductor device will be described with reference to FIGS. 6A to 6F.

<Structural Example of Semiconductor Device>

The structure of a semiconductor device manufactured in accordance witha method for manufacturing a semiconductor device of this embodiment isthe same as that of the transistor 120 of the above embodiment. In otherwords, the semiconductor device includes, over the substrate 100, theinsulating film 102, the source electrode 104 a, the drain electrode 104b, the oxide semiconductor film 108, the gate insulating film 110, andthe gate electrode 112 (see FIGS. 1A to 1C).

As described in the above embodiment, the oxide semiconductor film 108in the transistor 120 is an oxide semiconductor film subjected to oxygendoping treatment. Further, in this embodiment, oxygen doping treatmentis also performed on the insulating film 102 and the gate insulatingfilm 110. Such oxygen doping treatment enables the transistor 120 tohave higher reliability. In addition, the oxygen doping treatmentperformed on the insulating film 102 in this embodiment also serves as astep for removing a mask 103 a and a mask 103 b used for forming thesource electrode 104 a and the drain electrode 104 b. By employing sucha process, manufacturing cost can be reduced owing to simplification ofsteps. Note that in a similar to the above embodiment, transistorshaving different structures can also be manufactured (see FIGS. 3A to3D).

<Example of Manufacturing Process of Semiconductor Device>

An example of steps for manufacturing the semiconductor device will bedescribed below with reference to FIGS. 6A to 6F. Note that the basiccontents of the manufacturing steps are substantially the same as thoseof the above embodiments; therefore, only different points will bedescribed below.

First, the insulating film 102 is formed over the substrate 100 (seeFIG. 6A). The description of FIG. 4A can be referred to for the detailsthereof.

Next, a conductive film for forming the source electrode and the drainelectrode (including a wiring formed in the same layer as the sourceelectrode and the drain electrode) is formed over the insulating film102 and the conductive film is processed with the use of the mask 103 aand the mask 103 b, thereby forming the source electrode 104 a and thedrain electrode 104 b. Then, treatment using oxygen 180 a (also referredto as oxygen doping treatment or oxygen plasma doping treatment) isperformed on the insulating film 102 (see FIG. 6B). The description ofFIG. 4C can be referred to for the details of the steps for forming thesource electrode 104 a and the drain electrode 104 b. Here, the oxygendoping treatment also serves as the step for removing the mask 103 a andthe mask 103 b.

The oxygen 180 a contains at least any of an oxygen radical, an oxygenatom, and an oxygen ion. By performing oxygen doping treatment on theinsulating film 102, the oxygen can be contained in the insulating film102 and either or both in the oxide semiconductor film 108 formed lateror/and in the vicinity of the interface of the oxide semiconductor film108. In that case, the oxygen content is greater than the stoichiometricproportion of the insulating film 102, preferably greater than thestoichiometric proportion and less than four times the stoichiometricproportion, further preferably greater than the stoichiometricproportion and less than twice the stoichiometric proportion.Alternatively, the oxygen content may be greater than Y, preferablygreater than Y and less than 4Y, where the oxygen amount in the casewhere a material of the insulating film is single-crystalline is Y.Still alternatively, the oxygen content may be greater than Z,preferably greater than Z and less than 4Z based on the oxygen amount Zof the insulating film in the case where oxygen doping is not performed.

In the case of using a gallium oxide whose composition is expressed byGaO_(x) (x>0), a single crystal gallium oxide is Ga₂O₃; therefore, x canbe greater than 1.5 and less than 6 (i.e., the amount of O is greaterthan 1.5 times and less than 6 times that of Ga). Alternatively, in thecase of using a silicon oxide whose composition is expressed by SiO_(x)(x>0), when the silicon oxide is SiO₂ (i.e., the amount of O is twicethat of Si), x can be greater than 2 and less than 8 (i.e., the amountof O is greater than twice and less than 8 times that of Si). Such anexcessive oxygen region may exist in part of the insulating film(including the interface).

It is preferable that at least part of the oxygen 180 a added to theinsulating film have dangling bonds in the oxide semiconductor filmafter being supplied to the oxide semiconductor. This is because suchdangling bonds are linked with hydrogen remaining in the film so thathydrogen can be fixed (made to be immobile ions).

The oxygen 180 a can be generated by a plasma generating apparatus or anozone generating apparatus. Specifically, for example, the oxygen 180 ais generated with the use of an apparatus for ashing of a resist mask,or the like, and the insulating film 102 can be processed.

By the oxygen doping treatment, the mask 103 a and the mask 103 b areremoved. Note that, unlike a general step for removing a mask, the stepis performed to add oxygen; therefore, it is preferable that arelatively-strong bias be applied to the substrate.

In addition, by the oxygen doping treatment, a region containing oxygenat high concentration and a region containing oxygen at lowconcentration are formed in the insulating film 102. Specifically, inthe insulating film 102, a region which is not covered with the sourceelectrode 104 a and the drain electrode 104 b is the region containingoxygen at high concentration, and a region which is covered with thesource electrode 104 a and the drain electrode 104 b is the regioncontaining oxygen at low concentration.

Next, an oxide semiconductor film in contact with the source electrode104 a and the drain electrode 104 b is formed over the insulating film102 and the oxide semiconductor film is processed, so that anisland-shaped oxide semiconductor film is formed. Then, heat treatmentis performed on the island-shaped oxide semiconductor film, whereby thehighly-purified oxide semiconductor film 108 is formed (see FIG. 6C).The description of FIGS. 4D and 4E can be referred to for the details ofthe steps.

Then, the treatment using oxygen 180 b is performed on the oxidesemiconductor film 108 (see FIG. 6D). The description of FIG. 4F can bereferred to for the details thereof.

Next, the gate insulating film 110 which is in contact with part of theoxide semiconductor film 108 and covers the source electrode 104 a andthe drain electrode 104 b is formed. After that, treatment using oxygen180 c is performed on the gate insulating film 110 (see FIG. 6E). Thedescription of FIGS. 5A and 5B can be referred to for the detailsthereof.

Then, the gate electrode 112 is formed (see FIG. 6F). The description ofFIG. 5C can be referred to for the details thereof.

Note that an insulating film may be formed after formation of the gateelectrode 112. The insulating film may be formed using a silicon oxide,a silicon nitride, an aluminum oxide, an aluminum nitride, a galliumoxide, a mixed material of any of them, or the like. In particular, asilicon nitride film is preferable as the insulating film because dopedoxygen can be prevented from being released to the outside and entry ofhydrogen and the like to the oxide semiconductor film 108 from theoutside can be suppressed effectively. A wiring connected to the sourceelectrode 104 a, the drain electrode 104 b, the gate electrode 112, orthe like may be formed.

Through the above process, the transistor 120 is formed.

The example is described above in which oxygen doping treatment isperformed on all of the insulating film 102, the oxide semiconductorfilm 108, and the gate insulating film 110; however, one embodiment ofthe disclosed invention is not limited to this. For example, oxygendoping treatment may be performed on the insulating film 102 and theoxide semiconductor film 108.

The transistor according to this embodiment includes an oxidesemiconductor film highly purified to be electrically i-type (intrinsic)by removing impurities such as hydrogen, water, a hydroxyl group, andhydride (also referred to as a hydrogen compound) from the oxidesemiconductor and supplying oxygen which might be reduced in a step ofremoving impurities, through heat treatment. The transistor includingthe oxide semiconductor film highly purified in such a manner haselectrical characteristics such as the threshold voltage, which are lesslikely to change, and thus is electrically stable.

In particular, when the oxygen content in the oxide semiconductor filmis increased by oxygen doping treatment, deterioration due to electricalbias stress or heat stress can be suppressed and deterioration due tolight can be reduced.

In addition, according to the manufacturing method of this embodiment,the process is simplified and therefore, cost for manufacture can besuppressed.

As described above, according to an embodiment of the disclosedinvention, a transistor having excellent reliability can be providedwhile manufacturing cost is reduced.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

Embodiment 4

In this embodiment, an example of a plasma apparatus (also referred toas an ashing apparatus) which can be used for oxygen doping treatmentwill be described. Note that the apparatus is industrially suitable ascompared to an ion implantation apparatus or the like because theapparatus can be applicable for a large-sized glass substrate of thefifth generation or later, for example.

FIG. 17A illustrates an example of a top view of a single wafermulti-chamber equipment. FIG. 17B illustrates an example of across-sectional view of a plasma apparatus (also referred to as anashing apparatus) used for oxygen plasma doping.

The single wafer multi-chamber equipment illustrated in FIG. 17Aincludes three plasma apparatuses 10 each of which corresponds to FIG.17B, a substrate supply chamber 11 including three cassette ports 14 forholding a process substrate, a load lock chamber 12, a transfer chamber13, and the like. A substrate supplied to the substrate supply chamberis transferred through the load lock chamber 12 and the transfer chamber13 to a vacuum chamber 15 in the plasma apparatus 10 and is subjected tooxygen plasma doping. The substrate which has been subjected to oxygenplasma doping is transferred from the plasma apparatus 10, through theload lock chamber 12 and the transfer chamber 13, to the substratesupply chamber 11. Note that a transfer robot for transferring a processsubstrate is provided in each of the substrate supply chamber 11 and thetransfer chamber 13.

Referring to FIG. 17B, the plasma apparatus 10 includes the vacuumchamber 15. A plurality of gas outlets and an ICP coil (an inductivelycoupled plasma coil) 16 which is a generation source of plasma areprovided on a top portion of the vacuum chamber 15.

The twelve gas outlets are arranged in a center portion, seen from thetop of the plasma apparatus 10. Each of the gas outlets is connected toa gas supply source for supplying an oxygen gas, through a gas flow path17. The gas supply source includes a mass flow controller and the likeand can supply an oxygen gas to the gas flow path 17 at a desired flowrate (which is greater than 0 sccm and less than or equal to 1000 sccm).The oxygen gas supplied from the gas supply source is supplied from thegate flow path 17, through the twelve gas outlets, into the vacuumchamber 15.

The ICP coil 16 includes a plurality of strip-like conductors each ofwhich has a spiral form. One end of each of the conductors iselectrically connected to a first high-frequency power source 18 (13.56MHz) through a matching circuit for controlling impedance, and the otherend thereof is grounded.

A substrate stage 19 functioning as a bottom electrode is provided in alower portion of the vacuum chamber. By an electrostatic chuck or thelike provided for the substrate stage 19, a process substrate 20 is heldon the substrate stage so as to be detachable. The substrate stage 19 isprovided with a heater as a heating system and a He gas flow path as acooling system. The substrate stage is connected to a secondhigh-frequency power source 21 (3.2 MHz) for applying a substrate biasvoltage.

In addition, the vacuum chamber 15 is provided with an exhaust port andan automatic pressure control valve (also referred to as an APC) 22. TheAPC is connected to a turbo molecular pump 23 and further, connected toa dry pump 24 through the turbo molecular pump 23. The APC controls theinside pressure of the vacuum chamber. The turbo molecular pump 23 andthe dry pump 24 reduce the inside pressure of the vacuum chamber 15.

Next, described is an example in which plasma is generated in the vacuumchamber 15 illustrated in FIG. 17B, and oxygen plasma doping isperformed on an oxide semiconductor film, a base insulating film, or agate insulating film provided for the process substrate 20.

First, the inside pressure of the vacuum chamber 15 is held at a desiredpressure by operating the turbo molecular pump 23, the dry pump 24, andthe like, and then, the process substrate 20 is installed on thesubstrate stage in the vacuum chamber 15. Note that the processsubstrate 20 held on the substrate stage has at least an oxidesemiconductor film or a base insulating film. In this embodiment, theinside pressure of the vacuum chamber 15 is held at 1.33 Pa. Note thatthe flow rate of the oxygen gas supplied from the gas outlets into thevacuum chamber 15 is set at 250 sccm.

Next, a high-frequency power is applied from the first high-frequencypower source 18 to the ICP coil 16, thereby generating plasma. Then, astate in which plasma is being generated is kept for a certain period(greater than or equal to 30 seconds and less than or equal to 600seconds). Note that the high-frequency power applied to the ICP coil 16is greater than or equal to 1 kW and less than or equal to 10 kW. Inthis embodiment, the high-frequency power is set at 6000 W. At thistime, a substrate bias voltage may be applied from the secondhigh-frequency power source 21 to the substrate stage. In thisembodiment, the power used for applying the substrate bias voltage isset at 1000 W.

In this embodiment, the state in which plasma is being generated is keptfor 60 seconds and then, the process substrate 20 is transferred fromthe vacuum chamber 15. In this manner, oxygen plasma doping can beperformed on the oxide semiconductor film, the base insulating film, orthe gate insulating film provided for the process substrate 20.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

Embodiment 5

In this embodiment, as an example of a semiconductor device, a memorymedium (a memory element) will be described. In this embodiment, thetransistor including an oxide semiconductor described in any ofEmbodiments 1 to 3 or the like and a transistor including a materialother than an oxide semiconductor are formed over one substrate.

FIGS. 7A to 7C illustrate an example of a structure of a semiconductordevice. FIG. 7A is a cross-sectional view of the semiconductor device,and FIG. 7B is a plan view of the semiconductor device. Here, FIG. 7Acorresponds to a cross-sectional view along C1-C2 and D1-D2 of FIG. 7B.In addition, FIG. 7C illustrates an example of a diagram of a circuitincluding the semiconductor device as a memory element. In thesemiconductor device illustrated in FIGS. 7A and 7B, a transistor 240including a first semiconductor material is provided in a lower portion,and the transistor 120 described in Embodiment 1 is provided in an upperportion. Note that the transistor 120 includes a second semiconductormaterial as an oxide semiconductor. In this embodiment, the firstsemiconductor material is a semiconductor material other than an oxidesemiconductor. As the semiconductor material other than an oxidesemiconductor, for example, silicon, germanium, silicon germanium,silicon carbide, gallium arsenide, or the like can be used, and a singlecrystal semiconductor is preferably used. Alternatively, an organicsemiconductor material or the like may be used. A transistor includingsuch a semiconductor material other than an oxide semiconductor canoperate at high speed easily. On the other hand, a transistor includingan oxide semiconductor can hold charge for a long time owing to itscharacteristics.

Note that in this embodiment, an example in which the memory medium isformed using the transistor 120 is described; however, needless to say,any of the transistor 130, the transistor 140, the transistor 150, thetransistor 160, and the like described in Embodiment 1 or Embodiment 2can be used instead of the transistor 120.

The transistor 240 in FIGS. 7A to 7C includes a channel formation region216 provided in a substrate 200 including a semiconductor material(e.g., silicon), impurity regions 220 provided so as to sandwich thechannel formation region 216, metal compound regions in contact with theimpurity regions 220, a gate insulating film 208 provided over thechannel formation region 216, and the gate electrode 210 provided overthe gate insulating film 208.

As the substrate 200 including a semiconductor material, a singlecrystal semiconductor substrate or a polycrystalline semiconductorsubstrate of silicon, silicon carbide, or the like; a compoundsemiconductor substrate of silicon germanium or the like; an SOIsubstrate; or the like can be used. Note that although the term “SOIsubstrate” generally means a substrate in which a silicon semiconductorfilm is provided over an insulating surface, the term “SOI substrate” inthis specification and the like also includes a substrate in which asemiconductor film including a material other than silicon is providedover an insulating surface. In other words, a semiconductor filmincluded in the “SOI substrate” is not limited to a siliconsemiconductor film. Moreover, the SOI substrate can be a substrate inwhich a semiconductor film is provided over an insulating substrate suchas a glass substrate with an insulating film provided therebetween.

An element isolation insulating film 206 is provided over the substrate200 so as to surround the transistor 240, and an insulating film 228 andan insulating film 230 are provided to cover the transistor 240. Notethat for high integration, it is preferable that, as in FIG. 7A, thetransistor 240 does not have a sidewall insulating film. On the otherhand, in the case where the characteristics of the transistor 240 havepriority, sidewall insulating films may be provided on side surfaces ofthe gate electrode 210, and the impurity regions 220 may each include aregion with a different impurity concentration.

The transistor 240 can be manufactured using silicon, germanium, silicongermanium, silicon carbide, gallium arsenide, or the like. Such atransistor 240 is capable of high speed operation. Thus, when thetransistor is used as a reading transistor, data can be read out at highspeed.

After the transistor 240 is formed, as treatment prior to the formationof the transistor 120 and a capacitor 164, the insulating film 228 andthe insulating film 230 are subjected to CMP treatment so that a topsurface of the gate electrode 210 is exposed. As treatment for exposingthe top surface of the gate electrode 210, etching treatment, or thelike can also be employed instead of CMP treatment; in order to improvecharacteristics of the transistor 120, surfaces of the insulating film228 and the insulating film 230 are desirably made as flat as possible.

Next, a conductive film is formed over the gate electrode 210, theinsulating film 228, the insulating film 230, and the like and theconductive film is selectively etched, so that a source electrode 104 aand a drain electrode 104 b are formed.

The conductive film can be formed by a PVD method such as a sputteringmethod or a CVD method such as a plasma CVD method. As the material ofthe conductive film, an element selected from Al, Cr, Cu, Ta, Ti, Mo,and W, an alloy including any of the above elements as its component, orthe like can be used. Any of Mn, Mg, Zr, Be, Nd, and Sc, or a materialincluding any of these in combination may be used.

The conductive film may have either a single-layer structure or astacked structure of two or more layers. For example, the conductivefilm can have a single-layer structure of a titanium film or a titaniumnitride film, a single-layer structure of an aluminum film containingsilicon, a two-layer structure in which a titanium film is stacked overan aluminum film, a two-layer structure in which a titanium film isstacked over a titanium nitride film, or a three-layer structure inwhich a titanium film, an aluminum film, and a titanium film are stackedin this order. Note that in the case where the conductive film has asingle-layer structure of a titanium film or a titanium nitride film,there is an advantage that the source electrode 104 a and the drainelectrode 104 b can be easily processed to be tapered.

A channel length (L) of the transistor 120 in the upper portion isdetermined by a distance between a lower end portion of the sourceelectrode 104 a and a lower end portion of the drain electrode 104 b.Note that for light exposure for forming a mask used in the case where atransistor with a channel length (L) of less than 25 nm is formed, it isdesirable to use extreme ultraviolet whose wavelength is as short asseveral nanometers to several tens of nanometers.

Next, an oxide semiconductor film is formed to cover the sourceelectrode 104 a and the drain electrode 104 b, and the oxidesemiconductor film is selectively etched, so that the oxidesemiconductor film 108 is formed. The oxide semiconductor film is formedusing the material and the formation process described in Embodiment 1.

Then, a gate insulating film 110 in contact with the oxide semiconductorfilm 108 is formed. The gate insulating film 110 is formed using thematerial and the formation process described in Embodiment 1.

Next, over the gate insulating film 110, a gate electrode 112 a and anelectrode 112 b are formed so as to overlap with the oxide semiconductorfilm 108 and the source electrode 104 a, respectively.

After the gate insulating film 110 is formed, heat treatment (alsoreferred to as supply of oxygen) is desirably performed in an inert gasatmosphere or an oxygen atmosphere. The temperature of the heattreatment is higher than or equal to 200° C. and lower than or equal to450° C., desirably higher than or equal to 250° C. and lower than orequal to 350° C. For example, the heat treatment may be performed at250° C. for one hour in a nitrogen atmosphere. By performing the heattreatment, variation in electrical characteristics of the transistor canbe reduced.

Note that the timing of the heat treatment for supplying oxygen is notlimited thereto. For example, the heat treatment for supplying oxygenmay be performed after the gate electrode is formed. Alternatively, heattreatment for supplying oxygen may be performed following heat treatmentfor dehydration or the like; heat treatment for dehydration or the likemay also serve as heat treatment for supplying oxygen; or heat treatmentfor supplying oxygen may also serve as heat treatment for dehydration orthe like.

As described above, when heat treatment for dehydration or the like, andoxygen doping or heat treatment for supplying oxygen are performed, theoxide semiconductor film 108 can be highly purified so as to containimpurities as little as possible.

The gate electrode 112 a and the electrode 112 b can be formed in such amanner that a conductive film is formed over the gate insulating film110 and then etched selectively.

Next, an insulating film 151 and an insulating film 152 are formed overthe gate insulating film 110, the gate electrode 112 a, and theelectrode 112 b. The insulating film 151 and the insulating film 152 canbe formed by a sputtering method, a CVD method, or the like. Theinsulating film 151 and the insulating film 152 can be formed using amaterial including an inorganic insulating material such as a siliconoxide, a silicon oxynitride, a silicon nitride, a hafnium oxide, analuminum oxide, or a gallium oxide.

Next, an opening reaching the drain electrode 104 b is formed in thegate insulating film 110, the insulating film 151, and the insulatingfilm 152. The opening is formed by selective etching with the use of amask or the like.

After that, an electrode 154 is formed in the opening, and a wiring 156which is in contact with the electrode 154 is formed over the insulatingfilm 152.

The electrode 154 can be formed in such a manner, for example, that aconductive film is formed in a region including the opening by a PVDmethod, a CVD method, or the like and then part of the conductive filmis removed by etching, CMP, or the like.

The wiring 156 is formed in such a manner that a conductive film isformed by a PVD method such as a sputtering method or a CVD method suchas a plasma CVD method, and then the conductive film is patterned.Further, as a material of the conductive film, an element selected fromAl, Cr, Cu, Ta, Ti, Mo, and W, an alloy containing any of the aboveelements as its component, or the like can be used. Any of Mn, Mg, Zr,Be, Nd, and Sc, or a material including any of these in combination maybe used. The details are the same as those of the source electrode 104a, the drain electrode 104 b, or the like.

Through the above process, the transistor 120 and the capacitor 164which include the highly purified oxide semiconductor film 108 arecompleted. The capacitor 164 includes the source electrode 104 a, theoxide semiconductor film 108, the gate insulating film 110, and theelectrode 112 b.

Note that in the capacitor 164 in FIGS. 7A to 7C, insulation between thesource electrode 104 a and the electrode 112 b can be sufficientlysecured by stacking the oxide semiconductor film 108 and the gateinsulating film 110. Needless to say, the capacitor 164 without theoxide semiconductor film 108 may be employed in order to securesufficient capacitance. Further alternatively, the capacitor 164 may beomitted in the case where a capacitor is not needed.

FIG. 7C illustrates an example of a diagram of a circuit using thesemiconductor device as a memory element. In FIG. 7C, one of a sourceelectrode and a drain electrode of the transistor 120, one electrode ofthe capacitor 164, and a gate electrode of the transistor 240 areelectrically connected to each other. A first wiring (1st Line, alsoreferred to as a source line) is electrically connected to a sourceelectrode of the transistor 240. A second wiring (2nd Line, alsoreferred to as a bit line) is electrically connected to a drainelectrode of the transistor 240. A third wiring (3rd Line, also referredto as a first signal line) is electrically connected to the other of thesource electrode and the drain electrode of the transistor 120. A fourthwiring (4th Line, also referred to as a second signal line) iselectrically connected to a gate electrode of the transistor 120. Afifth wiring (5th Line, also referred to as a word line) is electricallyconnected to the other electrode of the capacitor 164.

The transistor 120 including an oxide semiconductor has an extremely lowoff current; therefore, when the transistor 120 is turned off, thepotential of a node (hereinafter, a node FG) where one of the sourceelectrode and drain electrode of the transistor 120, one electrode ofthe capacitor 164, and the gate electrode of the transistor 240 areelectrically connected to each other can be held for an extremely longtime. The capacitor 164 facilitates holding of charge given to the nodeFG and reading of the held data.

When data is stored in the semiconductor device (writing), first, thepotential of the fourth wiring is set to a potential at which thetransistor 120 is turned on, whereby the transistor 120 is turned on.Thus, the potential of the third wiring is applied to the node FG and apredetermined amount of charge is accumulated in the node FG. Here,charge for applying either of two different potential levels(hereinafter referred to as a low-level charge and a high-level charge)is given to the node FG. After that, the potential of the fourth wiringis set to a potential at which the transistor 120 is turned off, wherebythe transistor 120 is turned off. This makes the node FG floating andthe predetermined amount of charge remains held in the node FG. Thepredetermined amount of charge is thus accumulated and held in the nodeFG, whereby the memory cell can store data.

Since the off current of the transistor 120 is extremely small, thecharge applied to the node FG is held for a long time. This can removethe need of refresh operation or drastically reduce the frequency of therefresh operation, which leads to a sufficient reduction in powerconsumption. Moreover, stored data can be held for a long time even whenpower is not supplied.

When stored data is read out (reading), while a predetermined potential(a fixed potential) is applied to the first wiring, an appropriatepotential (a read-out potential) is applied to the fifth wiring, wherebythe transistor 240 changes its state depending on the amount of chargeheld in the node FG. This is because, in general, when the transistor240 is an re-channel transistor, an apparent threshold value V_(th) _(—)_(H) of the transistor 240 in the case where a high-level charge is heldin the node FG is lower than an apparent threshold value V_(th) _(—)_(L) of the transistor 240 in the case where a low-level charge is heldin the node FG. Here, an apparent threshold voltage refers to thepotential of the fifth wiring, which is needed to turn on the transistor240. Thus, by setting the potential of the fifth wiring to a potentialV_(o) which is between V_(th) _(—) _(H) and V_(th) _(—) _(L), chargeheld in the node FG can be determined. For example, in the case where ahigh-level charge is given in writing, when the potential of the fifthwiring is set to V₀ (>V_(th) _(—) _(H)), the transistor 240 is turnedon. In the case where a low-level charge is given in writing, even whenthe potential of the fifth wiring is set to V₀ (<V_(th) _(—) _(L)), thetransistor 240 remains in an off state. In such a manner, by controllingthe potential of the fifth wiring and determining whether the transistor240 is in an on state or off state (reading out the potential of thesecond wiring), stored data can be read out.

Further, in order to rewrite stored data, a new potential is applied tothe node FG that is holding the predetermined amount of charge given inthe above writing, so that the charge of the new data is held in thenode FG. Specifically, the potential of the fourth wiring is set to apotential at which the transistor 120 is turned on, whereby thetransistor 120 is turned on. Consequently, the potential of the thirdwiring (a potential of new data) is applied to the node FG, and thepredetermined amount of charge is accumulated in the node FG. Afterthat, the potential of the fourth wiring is set to a potential at whichthe transistor 120 is turned off, whereby the transistor 120 is turnedoff. Thus, charge of the new data is held in the node FG. In otherwords, while the predetermined amount of charge given in the firstwriting is held in the node FG, the same operation (a second writing) asthat in the first writing is performed, whereby the stored data can beoverwritten.

The off current of the transistor 120 described in this embodiment canbe sufficiently reduced by using the highly purified oxide and intrinsicsemiconductor film 108. In addition, when the oxide semiconductor film108 contains excessive oxygen, variation in the electricalcharacteristics of the transistor 120 is suppressed, so that thetransistor which is electrically stable can be obtained. Further, withthe use of such a transistor, a highly reliable semiconductor devicecapable of holding stored data for an extremely long time can beobtained.

In the semiconductor device described in this embodiment, the transistor240 and the transistor 120 overlap with each other; therefore, theintegration degree of the semiconductor device can be sufficiently high.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

Embodiment 6

A semiconductor device having a display function (also referred to as adisplay device) can be manufactured using any of the transistorsexemplified in Embodiments 1 to 3. Moreover, part or all of a drivercircuit which includes the transistor can be formed over a substratewhere the pixel portion is formed, whereby a system-on-panel can beobtained.

In FIG. 8A, a sealant 4005 is provided so as to surround a pixel portion4002 provided over a first substrate 4001, and the pixel portion 4002 issealed by using a second substrate 4006. In FIG. 8A, a signal linedriver circuit 4003 and a scan line driver circuit 4004 which are formedusing a single crystal semiconductor film or a polycrystallinesemiconductor film over a substrate separately prepared are mounted in aregion that is different from the region surrounded by the sealant 4005over the first substrate 4001. Various signals and potentials aresupplied to the signal line driver circuit 4003 and the scan line drivercircuit 4004 which are separately formed and the pixel portion 4002 fromflexible printed circuits (FPCs) 4018 a and 4018 b.

In FIGS. 8B and 8C, the sealant 4005 is provided so as to surround thepixel portion 4002 and the scan line driver circuit 4004 which areprovided over the first substrate 4001. The second substrate 4006 isprovided over the pixel portion 4002 and the scan line driver circuit4004. Consequently, the pixel portion 4002 and the scan line drivercircuit 4004 are sealed together with the display element, by the firstsubstrate 4001, the sealant 4005, and the second substrate 4006. InFIGS. 8B and 8C, the signal line driver circuit 4003 which is formedusing a single crystal semiconductor film or a polycrystallinesemiconductor film over a substrate prepared separately is mounted in aregion that is different from the region surrounded by the sealant 4005over the first substrate 4001. In FIGS. 8B and 8C, various signals andpotential are supplied to the signal line driver circuit 4003 which isseparately formed, the scan line driver circuit 4004, and the pixelportion 4002 from an FPC 4018.

An embodiment of the present invention is not limited to the structuresdescribed in FIGS. 8A to 8C. Only part of the signal line driver circuitor part of the scan line driver circuit may be separately formed andthen mounted.

Note that a connection method of a separately formed driver circuit isnot particularly limited, and a chip on glass (COG) method, a wirebonding method, a tape automated bonding (TAB) method or the like can beused. FIG. 8A illustrates an example in which the signal line drivercircuit 4003 and the scan line driver circuit 4004 are mounted by a COGmethod. FIG. 8B illustrates an example in which the signal line drivercircuit 4003 is mounted by a COG method. FIG. 8C illustrates an examplein which the signal line driver circuit 4003 is mounted by a TAB method.

In addition, the display device includes a panel in which the displayelement is sealed, and a module in which an IC or the like including acontroller is mounted on the panel.

Note that the display device in this specification means an imagedisplay device, a display device, or a light source (including alighting device). Furthermore, the display device also includes thefollowing modules in its category: a module to which a connector such asan FPC, a TAB tape, or a TCP is attached; a module having a TAB tape ora TCP at the tip of which a printed wiring board is provided; and amodule in which an integrated circuit (IC) is directly mounted on adisplay element by a COG method.

The pixel portion and the scan line driver circuit provided over thefirst substrate include a plurality of transistors, and any of thetransistors which are described in Embodiments 1 to 3 can be appliedthereto.

As the display element provided in the display device, a liquid crystalelement (also referred to as a liquid crystal display element) or alight-emitting element (also referred to as a light-emitting displayelement) can be used. The light-emitting element includes, in itscategory, an element whose luminance is controlled by a current or avoltage, and specifically includes, in its category, an inorganicelectroluminescent (EL) element, an organic EL element, and the like.Furthermore, a display medium whose contrast is changed by an electriceffect, such as electronic ink, can be used.

An embodiment of the semiconductor device is described with reference toFIG. 9, FIG. 10, and FIG. 11. FIG. 9, FIG. 10, and FIG. 11 correspond tocross-sectional views taken along line M-N in FIG. 8B.

As illustrated in FIG. 9 to FIG. 11, the semiconductor device includes aconnection terminal electrode 4015 and a terminal electrode 4016. Theconnection terminal electrode 4015 and the terminal electrode 4016 areelectrically connected to a terminal included in the FPC 4018 through ananisotropic conductive film 4019.

The connection terminal electrode 4015 is formed using the sameconductive film as a first electrode layer 4030, and the terminalelectrode 4016 is formed using the same conductive film as source anddrain electrodes of a transistor 4010 and a transistor 4011.

The pixel portion 4002 and the scan line driver circuit 4004 which areprovided over the first substrate 4001 include a plurality oftransistors. In FIG. 9 to FIG. 11, the transistor 4010 included in thepixel portion 4002 and the transistor 4011 included in the scan linedriver circuit 4004 are illustrated as an example. In FIG. 10 and FIG.11, an insulating layer 4021 is provided over the transistor 4010 andthe transistor 4011.

In this embodiment, the transistors described in any of Embodiments 1 to3 can be applied to the transistor 4010 and the transistor 4011.Variation in electrical characteristics of the transistor 4010 and thetransistor 4011 is suppressed and the transistor 4010 and the transistor4011 are electrically stable. Therefore, highly reliable semiconductordevices can be provided as the semiconductor devices illustrated in FIG.9 to FIG. 11.

The transistor 4010 provided in the pixel portion 4002 is electricallyconnected to a display element, in a display panel. A variety of displayelements can be used as the display element as long as display can beperformed.

An example of a liquid crystal display device using a liquid crystalelement as a display element is described in FIG. 9. In FIG. 9, a liquidcrystal element 4013 which is a display element includes the firstelectrode layer 4030, the second electrode layer 4031, and a liquidcrystal layer 4008. An insulating film 4032 and an insulating film 4033which serve as alignment films are provided so that the liquid crystallayer 4008 is provided therebetween. The second electrode layer 4031 isprovided on the second substrate 4006 side, and the first electrodelayer 4030 and the second electrode layer 4031 are stacked with theliquid crystal layer 4008 provided therebetween.

A columnar spacer 4035 is obtained by selective etching of an insulatingfilm and is provided in order to control the thickness (a cell gap) ofthe liquid crystal layer 4008. Note the spacer is not limited to acolumnar spacer, and, for example, a spherical spacer may be used.

In the case where a liquid crystal element is used as the displayelement, a thermotropic liquid crystal, a low-molecular liquid crystal,a high-molecular liquid crystal, a polymer dispersed liquid crystal, aferroelectric liquid crystal, an anti-ferroelectric liquid crystal, orthe like can be used. Such a liquid crystal material exhibits acholesteric phase, a smectic phase, a cubic phase, a chiral nematicphase, an isotropic phase, or the like depending on a condition.

Alternatively, liquid crystal exhibiting a blue phase for which analignment film is unnecessary may be used. A blue phase is one of liquidcrystal phases, which is generated just before a cholesteric phasechanges into an isotropic phase while temperature of cholesteric liquidcrystal is increased. Since the blue phase appears only in a narrowtemperature range, a liquid crystal composition in which several weightpercent or more of a chiral material is mixed is used for the liquidcrystal layer in order to improve the temperature range. The liquidcrystal composition which includes a liquid crystal showing a blue phaseand a chiral agent has a short response time of 1 msec or less, hasoptical isotropy, which makes the alignment process unneeded, and has asmall viewing angle dependence. In addition, since an alignment filmdoes not need to be provided and rubbing treatment is unnecessary,electrostatic discharge damage caused by the rubbing treatment can beprevented and defects and damage of the liquid crystal display devicecan be reduced in the manufacturing process. Thus, productivity of theliquid crystal display device can be increased.

The specific resistivity of the liquid crystal material is 1×10⁹ Ω·cm ormore, preferably 1×10¹¹ Ω·cm or more, more preferably 1×10¹² Ω·cm ormore. The value of the specific resistivity in this specification ismeasured at 20° C.

The size of a storage capacitor formed in the liquid crystal displaydevice is set considering the leakage current of the transistor providedin the pixel portion or the like so that charge can be held for apredetermined period. By using the transistor including the highlypurified oxide semiconductor film, it is enough to provide a storagecapacitor having a capacitance that is ⅓ or less, preferably ⅕ or lessof a liquid crystal capacitance of each pixel.

In the transistor used in this embodiment, which includes the highlypurified oxide semiconductor film, the current in an off state (the offcurrent) can be made small. Accordingly, an electrical signal such as animage signal can be held for a long period, and a writing interval canbe set long in an on state. Accordingly, the frequency of refreshoperation can be reduced, which leads to an effect of suppressing powerconsumption.

In addition, the transistor including the highly purified oxidesemiconductor film used in this embodiment can have relatively highfield-effect mobility and thus is capable of high speed operation.Therefore, by using the transistor in the pixel portion of the liquidcrystal display device, a high-quality image can be displayed. Inaddition, since the transistors can be separately provided in a drivercircuit portion and a pixel portion over one substrate, the number ofcomponents of the liquid crystal display device can be reduced.

For the liquid crystal display device, a twisted nematic (TN) mode, anin-plane-switching (IPS) mode, a fringe field switching (FFS) mode, anaxially symmetric aligned micro-cell (ASM) mode, an optical compensatedbirefringence (OCB) mode, a ferroelectric liquid crystal (FLC) mode, anantiferroelectric liquid crystal (AFLC) mode, or the like can be used.

A normally black liquid crystal display device such as a transmissiveliquid crystal display device utilizing a vertical alignment (VA) modemay be used. The vertical alignment mode is a method of controllingalignment of liquid crystal molecules of a liquid crystal display panel,in which liquid crystal molecules are aligned vertically to a panelsurface when no voltage is applied. Some examples are given as thevertical alignment mode. For example, a multi-domain vertical alignment(MVA) mode, a patterned vertical alignment (PVA) mode, an advanced superview (ASV) mode, or the like can be used. Moreover, it is possible touse a method called domain multiplication or multi-domain design, inwhich a pixel is divided into some regions (subpixels) and molecules arealigned in different directions in their respective regions.

In the display device, a black matrix (a light-blocking layer), anoptical member (an optical substrate) such as a polarizing member, aretardation member, or an anti-reflection member, and the like areprovided as appropriate. For example, circular polarization may beobtained by using a polarizing substrate and a retardation substrate. Inaddition, a backlight, a side light, or the like may be used as a lightsource.

In addition, it is possible to employ a time-division display method(also called a field-sequential driving method) with the use of aplurality of light-emitting diodes (LEDs) as a backlight. By employing afield-sequential driving method, color display can be performed withoutusing a color filter.

As a display method in the pixel portion, a progressive method, aninterlace method or the like can be employed. Further, color elementscontrolled in a pixel at the time of color display are not limited tothree colors of R, G, and B (R, G, and B correspond to red, green, andblue, respectively). For example, the following can be used: R, G, B,and W (W corresponds to white); R, G, B, and one or more of yellow,cyan, magenta, and the like; or the like. Further, the sizes of displayregions may be different between respective dots of the color elements.The present invention is not limited to the application to a displaydevice for color display but can also be applied to a display device formonochrome display.

Alternatively, as the display element included in the display device, alight-emitting element utilizing electroluminescence can be used.Light-emitting elements utilizing electroluminescence are classifieddepending on whether a light-emitting material is an organic compound oran inorganic compound. In general, the former is referred to as anorganic EL element, and the latter is referred to as an inorganic ELelement.

In an organic EL element, by application of voltage to a light-emittingelement, electrons and holes are injected from a pair of electrodes intoa layer containing a light-emitting organic compound, and current flows.The carriers (electrons and holes) are recombined, and thus, thelight-emitting organic compound is excited. The light-emitting organiccompound returns to a ground state from the excited state, therebyemitting light. Owing to such a mechanism, this light-emitting elementis referred to as a current-excitation light-emitting element.

The inorganic EL elements are classified depending on the elementstructure into a dispersion-type inorganic EL element and a thin-filminorganic EL element. A dispersion-type inorganic EL element has alight-emitting layer where particles of a light-emitting material aredispersed in a binder, and its light emission mechanism isdonor-acceptor recombination type light emission that utilizes a donorlevel and an acceptor level. A thin-film inorganic EL element has astructure where a light-emitting layer is sandwiched between dielectriclayers, which are further sandwiched between electrodes, and its lightemission mechanism is localized type light emission that utilizesinner-shell electron transition of metal ions. Note that an example ofan organic EL element as a light-emitting element is described here.

In order to extract light emitted from the light-emitting element, atleast one of a pair of electrodes is transparent. The transistor and thelight-emitting element are provided over the substrate. Thelight-emitting element can have a top emission structure in which lightemission is extracted through the surface opposite to the substrate; abottom emission structure in which light emission is extracted throughthe surface on the substrate side; or a dual emission structure in whichlight emission is extracted through the surface opposite to thesubstrate and the surface on the substrate side. A light-emittingelement having any of these emission structures can be used.

An example of a light-emitting device in which a light-emitting elementis used as a display element is illustrated in FIG. 10. A light-emittingelement 4513 which is a display element is electrically connected to thetransistor 4010 provided in the pixel portion 4002. A structure of thelight-emitting element 4513 is not limited to the stacked-layerstructure including the first electrode layer 4030, anelectroluminescent layer 4511, and the second electrode layer 4031,which is illustrated in FIG. 10. The structure of the light-emittingelement 4513 can be changed as appropriate depending on a direction inwhich light is extracted from the light-emitting element 4513, or thelike.

A partition wall 4510 is formed using an organic insulating material oran inorganic insulating material. It is particularly preferable that thepartition wall 4510 be formed using a photosensitive resin material tohave an opening over the first electrode layer 4030 so that a sidewallof the opening has a tilted surface with continuous curvature.

The electroluminescent layer 4511 may be formed using a single layer ora plurality of layers stacked.

A protective film may be formed over the second electrode layer 4031 andthe partition wall 4510 in order to prevent entry of oxygen, hydrogen,moisture, carbon dioxide, or the like into the light-emitting element4513. As the protective film, a silicon nitride film, a silicon nitrideoxide film, a diamond like carbon (DLC) film, or the like can be formed.In addition, in a space which is formed with the first substrate 4001,the second substrate 4006, and the sealant 4005, a filler 4514 isprovided for sealing. It is preferable that a panel be packaged (sealed)with a protective film (such as a laminate film or an ultravioletcurable resin film) or a cover material with high air-tightness andlittle degasification so that the panel is not exposed to the outsideair, in this manner.

As the filler 4514, an ultraviolet curable resin or a thermosettingresin can be used as well as an inert gas such as nitrogen or argon. Forexample, PVC (polyvinyl chloride), acrylic, polyimide, an epoxy resin, asilicone resin, PVB (polyvinyl butyral), or EVA (ethylene vinyl acetate)can be used. For example, nitrogen is used for the filler.

In addition, if needed, an optical film, such as a polarizing plate, acircularly polarizing plate (including an elliptically polarizingplate), a retardation plate (a quarter-wave plate or a half-wave plate),or a color filter, may be provided as appropriate for a light-emittingsurface of the light-emitting element. Further, the polarizing plate orthe circularly polarizing plate may be provided with an anti-reflectionfilm. For example, anti-glare treatment by which reflected light can bediffused by surface roughness so as to reduce the glare can beperformed.

Further, an electronic paper in which electronic ink is driven can beprovided as the display device. The electronic paper is also called anelectrophoretic display device (electrophoretic display) and hasadvantages in that it has the same level of readability as regularpaper, it has less power consumption than other display devices, and itcan be set to have a thin and light form.

An electrophoretic display device can have various modes. Anelectrophoretic display device contains a plurality of microcapsulesdispersed in a solvent or a solute, each microcapsule containing firstparticles which are positively charged and second particles which arenegatively charged. By applying an electric field to the microcapsules,the particles in the microcapsules move in opposite directions to eachother and only the color of the particles gathering on one side isdisplayed. Note that the first particles and the second particles eachcontain pigment and do not move without an electric field. Moreover, thefirst particles and the second particles have different colors (one ofwhich may be colorless).

Thus, an electrophoretic display device is a display device thatutilizes a so-called dielectrophoretic effect by which a substancehaving a high dielectric constant moves to a high-electric field region.

A solution in which the above microcapsules are dispersed in a solventis referred to as electronic ink. This electronic ink can be printed ona surface of glass, plastic, cloth, paper, or the like. Furthermore, byusing a color filter or particles that have a pigment, color display canalso be achieved.

Note that the first particles and the second particles in themicrocapsules may each be formed of a single material selected from aconductive material, an insulating material, a semiconductor material, amagnetic material, a liquid crystal material, a ferroelectric material,an electroluminescent material, an electrochromic material, and amagnetophoretic material, or formed of a composite material of any ofthese.

As the electronic paper, a display device using a twisting ball displaysystem can be used. The twisting ball display system refers to a methodin which spherical particles each colored in black and white arearranged between a first electrode layer and a second electrode layerwhich are electrode layers used for a display element, and a potentialdifference is generated between the first electrode layer and the secondelectrode layer to control orientation of the spherical particles, sothat display is performed.

FIG. 11 illustrates active matrix electronic paper as an embodiment of asemiconductor device. The electronic paper in FIG. 11 is an example of adisplay device using a twisting ball display system.

Between the first electrode layer 4030 connected to the transistor 4010and the second electrode layer 4031 provided for the second substrate4006, spherical particles 4613 each of which includes a black region4615 a, a white region 4615 b, and a cavity 4612 which is filled withliquid around the black region 4615 a and the white region 4615 b, areprovided. A space around the spherical particles 4613 is filled with afiller 4614 such as a resin. The second electrode layer 4031 correspondsto a common electrode (counter electrode). The second electrode layer4031 is electrically connected to a common potential line.

Note that in FIG. 9 to FIG. 11, a flexible substrate as well as a glasssubstrate can be used as any of the first substrate 4001 and the secondsubstrate 4006. For example, a plastic substrate havinglight-transmitting properties can be used. As plastic, afiberglass-reinforced plastics (FRP) plate, a polyvinyl fluoride (PVF)film, a polyester film, or an acrylic resin film can be used. Inaddition, a sheet with a structure in which an aluminum foil issandwiched between PVF films or polyester films can be used.

The insulating layer 4021 can be formed using an inorganic insulatingmaterial or an organic insulating material. Note that the insulatinglayer 4021 formed using a heat-resistant organic insulating materialsuch as an acrylic resin, polyimide, a benzocyclobutene-based resin,polyamide, or an epoxy resin is preferably used as a planarizinginsulating film. As well as such organic insulating materials, it ispossible to use a low-dielectric constant material (a low-k material), asiloxane based resin, phosphosilicate glass (PSG), borophosphosilicateglass (BPSG), or the like. The insulating layer may be formed bystacking a plurality of insulating films formed of these materials.

There is no particular limitation on the method for forming theinsulating layer 4021, and the insulating layer 4021 can be formed,depending on the material, by a sputtering method, a spin coatingmethod, a dipping method, spray coating, a droplet discharge method(e.g., an inkjet method), screen printing, offset printing, rollcoating, curtain coating, knife coating, or the like.

The display device displays an image by transmitting light from a lightsource or a display element. Therefore, the substrate and the thin filmssuch as the insulating film and the conductive film provided for thepixel portion where light is transmitted have light-transmittingproperties with respect to light in the visible-light wavelength range.

The first electrode layer and the second electrode layer (each of whichmay be called a pixel electrode layer, a common electrode layer, acounter electrode layer, or the like) for applying voltage to thedisplay element may have light-transmitting properties orlight-reflecting properties, which depends on the direction in whichlight is extracted, the position where the electrode layer is provided,the pattern structure of the electrode layer, and the like.

The first electrode layer 4030 and the second electrode layer 4031 canbe formed using a light-transmitting conductive material such as indiumoxide containing tungsten oxide, indium zinc oxide containing tungstenoxide, indium oxide containing titanium oxide, indium tin oxidecontaining titanium oxide, indium tin oxide (hereinafter referred to asITO), indium zinc oxide, or indium tin oxide to which silicon oxide isadded.

The first electrode layer 4030 and the second electrode layer 4031 canbe formed of one or more kinds using materials selected from metals suchas tungsten (W), molybdenum (Mo), zirconium (Zr), hafnium (Hf), vanadium(V), niobium (Nb), tantalum (Ta), chromium (Cr), cobalt (Co), nickel(Ni), titanium (Ti), platinum (Pt), aluminum (Al), copper (Cu), andsilver (Ag); alloys of these metals; and nitrides of these metals.

Since the transistor is easily broken owing to static electricity or thelike, a protective circuit for protecting the driver circuit ispreferably provided. The protective circuit is preferably formed using anon-linear element.

As described above, by using any of the transistors exemplified inEmbodiments 1 to 3, a highly reliable semiconductor device can beprovided.

This embodiment can be implemented in appropriate combination with anyof the structures described in the other embodiments.

Embodiment 7

A semiconductor device having an image sensor function for reading dataof an object can be formed with the use of any of the transistorsdescribed in Embodiments 1 to 3.

An example of a semiconductor device having an image sensor function isillustrated in FIG. 12A. FIG. 12A illustrates an equivalent circuit of aphoto sensor, and FIG. 12B is a cross-sectional view illustrating partof the photo sensor.

In a photodiode 602, one electrode is electrically connected to aphotodiode reset signal line 658, and the other electrode iselectrically connected to a gate of a transistor 640. One of a sourceand a drain of the transistor 640 is electrically connected to a photosensor reference signal line 672, and the other of the source and thedrain thereof is electrically connected to one of a source and a drainof a transistor 656. A gate of the transistor 656 is electricallyconnected to a gate signal line 659, and the other of the source and thedrain thereof is electrically connected to a photo sensor output signalline 671.

Note that in circuit diagrams in this specification, a transistorincluding an oxide semiconductor film is denoted by a symbol “OS” sothat it can be identified as a transistor including an oxidesemiconductor film. The transistor 640 and the transistor 656 in FIG.12A are transistors each including an oxide semiconductor film.

FIG. 12B is a cross-sectional view of the photodiode 602 and thetransistor 640 in the photo sensor. The photodiode 602 functioning as asensor and the transistor 640 are provided over a substrate 601 (a TFTsubstrate) having an insulating surface. A substrate 613 is providedover the photodiode 602 and the transistor 640 with an adhesive layer608 provided therebetween. In addition, an insulating film 631, a firstinterlayer insulating layer 633, and a second interlayer insulatinglayer 634 are provided over the transistor 640.

Further, a gate electrode 645 is provided in the same layer as the gateelectrode of the transistor 640 so as to be electrically connected tothe gate electrode of the transistor 640. The gate electrode 645 iselectrically connected to an electrode layer 641 through an openingprovided in the insulating film 631 and the first interlayer insulatinglayer 633. The electrode layer 641 is electrically connected to aconductive layer 643 formed in the second interlayer insulating layer634, and an electrode layer 642 is electrically connected to the gateelectrode 645 through the electrode layer 641; accordingly, thephotodiode 602 is electrically connected to the transistor 640.

The photodiode 602 is provided over the first interlayer insulatinglayer 633. In the photodiode 602, a first semiconductor layer 606 a, asecond semiconductor layer 606 b, and a third semiconductor layer 606 care sequentially stacked from the first interlayer insulating layer 633side, between the electrode layer 641 formed over the first interlayerinsulating layer 633 and the electrode layer 642 formed over the secondinterlayer insulating layer 634.

In this embodiment, any of the transistors described in Embodiments 1 to3 can be applied to the transistor 640. The transistor 640 and thetransistor 656 have suppressed variation in electrical characteristicsand are electrically stable. Therefore, a highly reliable semiconductordevice can be provided as the semiconductor device of this embodimentdescribed in FIGS. 12A and 12B.

Here, a pin photodiode in which a semiconductor layer having a p-typeconductivity as the first semiconductor layer 606 a, a high-resistancesemiconductor layer (i-type semiconductor layer) as the secondsemiconductor layer 606 b, and a semiconductor layer having an n-typeconductivity as the third semiconductor layer 606 c are stacked isillustrated as an example.

The first semiconductor layer 606 a is a p-type semiconductor layer andcan be formed using an amorphous silicon film containing an impurityelement imparting a p-type conductivity. The first semiconductor layer606 a is formed by a plasma CVD method with use of a semiconductorsource gas containing an impurity element belonging to Group 13 (such asboron (B)). As the semiconductor source gas, silane (SiH₄) may be used.Alternatively, Si₂H₆, SiH₂Cl₂, SiHCl₃, SiCl₄, SiF₄, or the like may beused. Further alternatively, an amorphous silicon film which does notcontain an impurity element may be formed, and then, an impurity elementmay be introduced to the amorphous silicon film with use of a diffusionmethod or an ion implantation method. Heating or the like may beconducted after introducing the impurity element by an ion implantationmethod or the like in order to diffuse the impurity element. In thatcase, as a method of forming the amorphous silicon film, an LPCVDmethod, a chemical vapor deposition method, a sputtering method, or thelike may be used. The first semiconductor layer 606 a is preferablyformed to have a thickness greater than or equal to 10 nm and less thanor equal to 50 nm.

The second semiconductor layer 606 b is an i-type semiconductor layer(intrinsic semiconductor layer) and is formed using an amorphous siliconfilm. As for formation of the second semiconductor layer 606 b, anamorphous silicon film is formed with use of a semiconductor source gasby a plasma CVD method. As the semiconductor source gas, silane (SiH₄)may be used. Alternatively, Si₂H₆, SiH₂Cl₂, SiHCl₃, SiCl₄, SiF₄, or thelike may be used. The second semiconductor layer 606 b may be formed byan LPCVD method, a vapor deposition method, a sputtering method, or thelike. The second semiconductor layer 606 b is preferably formed to havea thickness greater than or equal to 200 nm and less than or equal to1000 nm.

The third semiconductor layer 606 c is an n-type semiconductor layer andis formed using an amorphous silicon film containing an impurity elementimparting an n-type conductivity. The third semiconductor layer 606 c isformed by a plasma CVD method with use of a semiconductor source gascontaining an impurity element belonging to Group 15 (e.g., phosphorus(P)). As the semiconductor source gas, silane (SiH₄) may be used.Alternatively, Si₂H₆, SiH₂Cl₂, SiHCl₃, SiCl₄, SiF₄, or the like may beused. Further alternatively, an amorphous silicon film which does notcontain an impurity element may be formed, and then, an impurity elementmay be introduced to the amorphous silicon film with use of a diffusionmethod or an ion implantation method. Heating or the like may beconducted after introducing the impurity element by an ion injectingmethod or the like in order to diffuse the impurity element. In thatcase, as a method of forming the amorphous silicon film, an LPCVDmethod, a chemical vapor deposition method, a sputtering method, or thelike may be used. The third semiconductor layer 606 c is preferablyformed to have a thickness greater than or equal to 20 nm and less thanor equal to 200 nm.

The first semiconductor layer 606 a, the second semiconductor layer 606b, and the third semiconductor layer 606 c are not necessarily formedusing an amorphous semiconductor, and may be formed using apolycrystalline semiconductor, or a micro crystalline semiconductor (asemi-amorphous semiconductor: SAS).

The microcrystalline semiconductor belongs to a metastable state of anintermediate between amorphous and single crystalline when Gibbs freeenergy is considered. That is, the microcrystalline semiconductor is asemiconductor having a third state which is thermodynamically stable andhas a short range order and lattice distortion. Columnar-like orneedle-like crystals grow in a normal direction with respect to asubstrate surface. The Raman spectrum of microcrystalline silicon, whichis a typical example of a microcrystalline semiconductor, is located inlower wave numbers than 520 cm⁻¹, which represents a peak of the Ramanspectrum of single crystal silicon. That is, the peak of the Ramanspectrum of the microcrystalline silicon exists between 520 cm⁻¹ whichrepresents single crystal silicon and 480 cm⁻¹ which representsamorphous silicon. The semiconductor contains hydrogen or halogen of atleast 1 at. % to terminate a dangling bond. Moreover, microcrystallinesilicon is made to contain a rare gas element such as helium, neon,argon, or krypton to further enhance lattice distortion, wherebystability is increased and a favorable microcrystalline semiconductorfilm can be obtained.

The microcrystalline semiconductor film can be formed by ahigh-frequency plasma CVD method with a frequency of several tens ofmegahertz to several hundreds of megahertz or using a microwave plasmaCVD apparatus with a frequency of 1 GHz or more. Typically, themicrocrystalline semiconductor film can be formed by using a gasobtained by diluting SiH₄, Si₂H₆, SiH₂Cl₂, SiHCl₃, SiCl₄, or SiF₄, withhydrogen. Further, with a dilution with one or plural kinds of rare gaselements selected from helium, neon, argon, and krypton in addition tosilicon hydride and hydrogen, the microcrystalline semiconductor filmcan be formed. In that case, the flow ratio of hydrogen to siliconhydride is 5:1 to 200:1, preferably 50:1 to 150:1, more preferably100:1. Further, a carbide gas such as CH₄ or C₂H₆, a germanium gas suchas GeH₄ or GeF₄, F₂, or the like may be mixed into the gas containingsilicon.

In addition, since the mobility of holes generated by a photoelectriceffect is lower than that of electrons, a pin photodiode exhibits bettercharacteristics when a surface on the p-type semiconductor layer side isused as a light-receiving plane. Here, an example in which light 622received by the photodiode 602 from a surface of the substrate 601, overwhich the pin photodiode is formed, is converted into electric signalswill be described. Further, light from the semiconductor layer having aconductivity type opposite from that of the semiconductor layer on thelight-receiving plane is disturbance light; therefore, the electrodelayer 642 on the semiconductor layer having the opposite conductivitytype is preferably formed from a light-blocking conductive film. Notethat a surface of the n-type semiconductor layer side can alternativelybe used as the light-receiving plane.

For reduction of the surface roughness, an insulating layer functioningas a planarizing insulating film is preferably used as the firstinterlayer insulating layer 633 and the second interlayer insulatinglayer 634. The first interlayer insulating layer 633 and the secondinterlayer insulating layer 634 can be formed using, for example, anorganic insulating material such as polyimide, an acrylic resin, abenzocyclobutene-based resin, polyamide, or an epoxy resin. As well assuch organic insulating materials, it is possible to use a single layeror stacked layers of a low-dielectric constant material (a low-kmaterial), a siloxane-based resin, phosphosilicate glass (PSG),borophosphosilicate glass (BPSG), or the like.

The insulating film 631, the first interlayer insulating layer 633, andthe second interlayer insulating layer 634 can be formed using aninsulating material by a sputtering method, a spin coating method, adipping method, spray coating, a droplet discharge method (e.g., aninkjet method, screen printing, or offset printing), roll coating,curtain coating, knife coating, or the like depending on the material.

When the light 622 that enters the photodiode 602 is detected, data onan object to be detected can be read. Note that a light source such as abacklight can be used at the time of reading data on the object.

Any of the transistors described in Embodiments 1 to 3 can be used asthe transistor 640. The transistor including the oxide semiconductorfilm which is highly purified by intentionally removing an impurity suchas hydrogen, moisture, a hydroxyl group, or hydride (also referred to asa hydrogen compound) and contains excessive oxygen supplied by oxygendoping has electrical characteristics such as the threshold voltage,which are less likely to change, and thus is electrically stable.Therefore, a highly reliable semiconductor device can be provided.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

Embodiment 8

A semiconductor device disclosed in this specification can be applied toa variety of electronic appliances (including game machines). Examplesof electronic appliances are a television set (also referred to as atelevision or a television receiver), a monitor of a computer or thelike, a camera such as a digital camera or a digital video camera, adigital photo frame, a mobile phone handset (also referred to as amobile phone or a mobile phone device), a portable game machine, aportable information terminal, an audio reproducing device, alarge-sized game machine such as a pachinko machine, and the like.Examples of electronic appliances each including the liquid crystaldisplay device described in the above embodiment will be described.

FIG. 13A illustrates an electronic book reader (also referred to as ane-book reader) which can include housings 9630, a display portion 9631,operation keys 9632, a solar cell 9633, and a charge and dischargecontrol circuit 9634. The electronic book reader illustrated in FIG. 13Ahas a function of displaying various kinds of information (e.g., a stillimage, a moving image, and a text image) on the display portion, afunction of displaying a calendar, a date, the time, or the like on thedisplay portion, a function of operating or editing the informationdisplayed on the display portion, a function of controlling processingby various kinds of software (programs), and the like. Note that in FIG.13A, the charge and discharge control circuit 9634 has a battery 9635and a DCDC converter (hereinafter, abbreviated as a converter) 9636. Thesemiconductor device described in any of the above embodiments can beapplied to the display portion 9631, whereby the electronic book readercan be highly reliable.

In the case where a transflective liquid crystal display device or areflective liquid crystal display device is used as the display portion9631, use under a relatively bright condition is assumed; therefore, thestructure illustrated in FIG. 13A is preferable because power generationby the solar cell 9633 and charge with the battery 9635 are effectivelyperformed. Since the solar cell 9633 can be provided in a space (asurface or a rear surface) of the housing 9630 as appropriate, thebattery 9635 can be efficiently charged, which is preferable. When alithium ion battery is used as the battery 9635, there is an advantageof downsizing or the like.

The structure and the operation of the charge and discharge controlcircuit 9634 illustrated in FIG. 13A will be described with reference toa block diagram in FIG. 13B. The solar cell 9633, the battery 9635, theconverter 9636, a converter 9637, switches SW1 to SW3, and the displayportion 9631 are shown in FIG. 13B, and the battery 9635, the converter9636, the converter 9637, and the switches SW1 to SW3 are included inthe charge and discharge control circuit 9634.

First, an example of operation in the case where power is generated bythe solar cell 9633 using external light is described. The voltage ofpower generated by the solar cell is raised or lowered by the converter9636 to a voltage for charging the battery 9635. Then, when the powerfrom the solar cell 9633 is used for the operation of the displayportion 9631, the switch SW1 is turned on and the voltage of the poweris raised or lowered by the converter 9637 to a voltage needed for thedisplay portion 9631. In addition, when display on the display portion9631 is not performed, for example, the switch SW1 is turned off and theswitch SW2 is turned on so that the battery 9635 is charged.

Next, operation in the case where power is not generated by the solarcell 9633 using external light is described. The voltage of poweraccumulated in the battery 9635 is raised or lowered by the converter9637 by turning on the switch SW3. Then, power from the battery 9635 isused for the operation of the display portion 9631.

Note that although the solar cell 9633 is described as an example of ameans for charge, the battery 9635 may be charged with another means. Inaddition, a combination of the solar cell 9633 and another means forcharge may be used.

FIG. 14A illustrates a laptop personal computer, which includes a mainbody 3001, a housing 3002, a display portion 3003, a keyboard 3004, andthe like. By applying the semiconductor device described in any of theabove embodiments to the display portion 3003, the laptop personalcomputer can be highly reliable.

FIG. 14B is a personal digital assistant (PDA), which includes a mainbody 3021 provided with a display portion 3023, an external interface3025, operation buttons 3024, and the like. A stylus 3022 is included asan accessory for operation. By applying the semiconductor devicedescribed in any of the above embodiments to the display portion 3023,the personal digital assistant (PDA) can be highly reliable.

FIG. 14C illustrates an example of an electronic book reader. Forexample, an electronic book reader 2700 includes two housings, i.e., ahousing 2701 and a housing 2703. The housing 2701 and the housing 2703are combined with a hinge 2711 so that the electronic book reader 2700can be opened and closed with the hinge 2711 as an axis. With such astructure, the electronic book reader 2700 can operate like a paperbook.

A display portion 2705 and a display portion 2707 are incorporated inthe housing 2701 and the housing 2703, respectively. The display portion2705 and the display portion 2707 may display one image or differentimages. In the structure where different images are displayed ondifferent display portions, for example, the right display portion (thedisplay portion 2705 in FIG. 14C) displays text and the left displayportion (the display portion 2707 in FIG. 14C) displays images. Byapplying the semiconductor devices described in any of the aboveembodiments to the display portions 2705 and 2707, the electronic bookreader 2700 can be highly reliable.

FIG. 14C illustrates an example in which the housing 2701 is providedwith an operation portion and the like. For example, the housing 2701 isprovided with a power switch 2721, operation keys 2723, a speaker 2725,and the like. With the operation keys 2723, pages can be turned. Notethat a keyboard, a pointing device, or the like may also be provided onthe surface of the housing, on which the display portion is provided.Furthermore, an external connection terminal (an earphone terminal, aUSB terminal, or the like), a recording medium insertion portion, andthe like may be provided on the back surface or the side surface of thehousing. Moreover, the electronic book reader 2700 may have a functionof an electronic dictionary.

The electronic book reader 2700 may have a structure capable ofwirelessly transmitting and receiving data. Through wirelesscommunication, desired book data or the like can be purchased anddownloaded from an electronic book server.

FIG. 14D illustrates a mobile phone, which includes two housings, i.e.,a housing 2800 and a housing 2801. The housing 2801 includes a displaypanel 2802, a speaker 2803, a microphone 2804, a pointing device 2806, acamera lens 2807, an external connection terminal 2808, and the like. Inaddition, the housing 2800 includes a solar cell 2810 having a functionof charge of the mobile phone, an external memory slot 2811, and thelike. An antenna is incorporated in the housing 2801. By applying thesemiconductor device described in any of the above embodiments to thedisplay panel 2802, the mobile phone can be highly reliable.

Further, the display panel 2802 is provided with a touch panel. Aplurality of operation keys 2805 which is displayed as images isillustrated by dashed lines in FIG. 14D. Note that a boosting circuit bywhich a voltage output from the solar cell 2810 is increased to besufficiently high for each circuit is also provided.

On the display panel 2802, the display direction can be appropriatelychanged depending on a usage pattern. Further, the mobile phone isprovided with the camera lens 2807 on the same surface as the displaypanel 2802, and thus it can be used as a video phone. The speaker 2803and the microphone 2804 can be used for videophone calls, recording andplaying sound, and the like as well as voice calls. Furthermore, thehousings 2800 and 2801 which are developed as illustrated in FIG. 14Dcan overlap with each other by sliding; thus, the size of the mobilephone can be decreased, which makes the mobile phone suitable for beingcarried.

The external connection terminal 2808 can be connected to an AC adapterand various types of cables such as a USB cable, and charging and datacommunication with a personal computer are possible. Moreover, a largeamount of data can be stored by inserting a storage medium into theexternal memory slot 2811 and can be moved.

Further, in addition to the above functions, an infrared communicationfunction, a television reception function, or the like may be provided.

FIG. 14E illustrates a digital video camera which includes a main body3051, a display portion A 3057, an eyepiece portion 3053, an operationswitch 3054, a display portion B 3055, a battery 3056, and the like. Byapplying the semiconductor device described in any the above embodimentsto the display portion A 3057 and the display portion B 3055, thedigital video camera can be highly reliable.

FIG. 14F illustrates an example of a television device. In a televisionset 9600, a display portion 9603 is incorporated in a housing 9601. Thedisplay portion 9603 can display images. Here, the housing 9601 issupported by a stand 9605. By applying the semiconductor devicedescribed in any of the above embodiments to the display portion 9603,the television set 9600 can be highly reliable.

The television set 9600 can be operated by an operation switch of thehousing 9601 or a separate remote controller. Further, the remotecontroller may be provided with a display portion for displaying dataoutput from the remote controller.

Note that the television set 9600 is provided with a receiver, a modem,and the like. With the use of the receiver, general televisionbroadcasting can be received. Moreover, when the display device isconnected to a communication network with or without wires via themodem, one-way (from a sender to a receiver) or two-way (between asender and a receiver or between receivers) information communicationcan be performed.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

This application is based on Japanese Patent Application serial no.2010-100197 filed with the Japan Patent Office on Apr. 23, 2010, theentire contents of which are hereby incorporated by reference.

1. A semiconductor device comprising: an oxide semiconductor layercomprising a channel formation region, the oxide semiconductor layercomprising oxygen and metal elements, the metal elements includingindium; a metal oxide layer on and in contact with the oxidesemiconductor layer; an insulating layer comprising silicon and oxygenover the metal oxide layer; and a gate electrode adjacent to the oxidesemiconductor layer, wherein the metal oxide layer comprises oxygen andsame metal elements as the metal elements of the oxide semiconductorlayer, and wherein the metal oxide layer reduces an amount of oxygenvacancy which is associated with a bond between indium and oxygen. 2.The semiconductor device according to claim 1, wherein the metal oxidelayer is insulating.
 3. The semiconductor device according to claim 1,wherein the gate electrode is located over the oxide semiconductorlayer.
 4. The semiconductor device according to claim 1, wherein themetal oxide layer comprises gallium and oxygen.
 5. The semiconductordevice according to claim 1, wherein at least part of the metal oxidelayer comprises oxygen at a concentration higher than a stoichiometricratio in order to reduce an amount of oxygen vacancy which is associatedwith a bond between indium and oxygen.
 6. The semiconductor deviceaccording to claim 1, wherein at least part of the oxide semiconductorlayer comprises oxygen at a concentration higher than a stoichiometricratio in order to reduce an amount of oxygen vacancy which is associatedwith a bond between indium and oxygen.
 7. A semiconductor devicecomprising: an oxide semiconductor layer comprising a channel formationregion, the oxide semiconductor layer comprising oxygen, indium, zincand gallium; a metal oxide layer on and in contact with the oxidesemiconductor layer; an insulating layer comprising silicon and oxygenover the metal oxide layer; and a gate electrode adjacent to the oxidesemiconductor layer, wherein the metal oxide layer comprises oxygen,indium, zinc and gallium, and wherein the metal oxide layer reduces anamount of oxygen vacancy which is associated with a bond between indiumand oxygen.
 8. The semiconductor device according to claim 7, whereinthe metal oxide layer is insulating.
 9. The semiconductor deviceaccording to claim 7, wherein the gate electrode is located over theoxide semiconductor layer.
 10. The semiconductor device according toclaim 7, wherein at least part of the metal oxide layer comprises oxygenat a concentration higher than a stoichiometric ratio in order to reducean amount of oxygen vacancy which is associated with a bond betweenindium and oxygen.
 11. The semiconductor device according to claim 7,wherein at least part of the oxide semiconductor layer comprises oxygenat a concentration higher than a stoichiometric ratio in order to reducean amount of oxygen vacancy which is associated with a bond betweenindium and oxygen.
 12. A semiconductor device comprising: an oxidesemiconductor layer comprising a channel formation region, the oxidesemiconductor layer comprising oxygen and metal elements, the metalelements including indium; a metal oxide layer on and in contact withthe oxide semiconductor layer; an insulating layer comprising siliconand oxygen over the metal oxide layer; and a gate electrode adjacent tothe oxide semiconductor layer, wherein the metal oxide layer comprisesoxygen and at least one of the metal elements of the oxide semiconductorlayer, and wherein the metal oxide layer reduces an amount of oxygenvacancy which is associated with a bond between indium and oxygen. 13.The semiconductor device according to claim 12, wherein the metal oxidelayer is insulating.
 14. The semiconductor device according to claim 12,wherein the gate electrode is located over the oxide semiconductorlayer.
 15. The semiconductor device according to claim 12, wherein themetal oxide layer comprises gallium and oxygen.
 16. The semiconductordevice according to claim 12, wherein at least part of the metal oxidelayer comprises oxygen at a concentration higher than a stoichiometricratio in order to reduce an amount of oxygen vacancy which is associatedwith a bond between indium and oxygen.
 17. The semiconductor deviceaccording to claim 12, wherein at least part of the oxide semiconductorlayer comprises oxygen at a concentration higher than a stoichiometricratio in order to reduce an amount of oxygen vacancy which is associatedwith a bond between indium and oxygen.
 18. A semiconductor devicecomprising: an oxide semiconductor layer comprising a channel formationregion, the oxide semiconductor layer comprising oxygen and metalelements, the metal elements including indium; a metal oxide layer onand in contact with the oxide semiconductor layer; an insulating layercomprising silicon and oxygen over the metal oxide layer; and a gateelectrode adjacent to the oxide semiconductor layer, wherein the metaloxide layer comprises oxygen and gallium, and wherein the metal oxidelayer reduces an amount of oxygen vacancy which is associated with abond between indium and oxygen.
 19. The semiconductor device accordingto claim 18, wherein the metal oxide layer is insulating.
 20. Thesemiconductor device according to claim 18, wherein the gate electrodeis located over the oxide semiconductor layer.
 21. The semiconductordevice according to claim 18, wherein at least part of the metal oxidelayer comprises oxygen at a concentration higher than a stoichiometricratio in order to reduce an amount of oxygen vacancy which is associatedwith a bond between indium and oxygen.
 22. The semiconductor deviceaccording to claim 18, wherein at least part of the oxide semiconductorlayer comprises oxygen at a concentration higher than a stoichiometricratio in order to reduce an amount of oxygen vacancy which is associatedwith a bond between indium and oxygen.
 23. A semiconductor devicecomprising: an oxide semiconductor layer comprising a channel formationregion, the oxide semiconductor layer comprising oxygen and metalelements, the metal elements including indium; a metal oxide layer onand in contact with the oxide semiconductor layer; an insulating layercomprising silicon and oxygen over the metal oxide layer; and a gateelectrode adjacent to the oxide semiconductor layer, wherein the metaloxide layer comprises oxygen and same metal elements as the metalelements of the oxide semiconductor layer, and wherein the oxidesemiconductor layer comprises excessive oxygen to reduce an amount ofoxygen vacancy which is associated with a bond between indium andoxygen.
 24. The semiconductor device according to claim 23, wherein themetal oxide layer is insulating.
 25. The semiconductor device accordingto claim 23, wherein the gate electrode is located over the oxidesemiconductor layer.
 26. The semiconductor device according to claim 23,wherein the metal oxide layer comprises gallium and oxygen.
 27. Thesemiconductor device according to claim 23, wherein at least part of themetal oxide layer comprises oxygen at a concentration higher than astoichiometric ratio in order to reduce an amount of oxygen vacancywhich is associated with a bond between indium and oxygen.
 28. Thesemiconductor device according to claim 23, wherein at least part of theoxide semiconductor layer comprises oxygen at a concentration higherthan a stoichiometric ratio in order to reduce an amount of oxygenvacancy which is associated with a bond between indium and oxygen.
 29. Asemiconductor device comprising: an oxide semiconductor layer comprisinga channel formation region, the oxide semiconductor layer comprisingoxygen, indium, zinc and gallium; a metal oxide layer on and in contactwith the oxide semiconductor layer; an insulating layer comprisingsilicon and oxygen over the metal oxide layer; and a gate electrodeadjacent to the oxide semiconductor layer, wherein the metal oxide layercomprises oxygen, indium, zinc and gallium, and wherein the oxidesemiconductor layer comprises excessive oxygen to reduce an amount ofoxygen vacancy which is associated with a bond between indium andoxygen.
 30. The semiconductor device according to claim 29, wherein themetal oxide layer is insulating.
 31. The semiconductor device accordingto claim 29, wherein the gate electrode is located over the oxidesemiconductor layer.
 32. The semiconductor device according to claim 29,wherein at least part of the metal oxide layer comprises oxygen at aconcentration higher than a stoichiometric ratio in order to reduce anamount of oxygen vacancy which is associated with a bond between indiumand oxygen.
 33. The semiconductor device according to claim 29, whereinat least part of the oxide semiconductor layer comprises oxygen at aconcentration higher than a stoichiometric ratio in order to reduce anamount of oxygen vacancy which is associated with a bond between indiumand oxygen.
 34. A semiconductor device comprising: an oxidesemiconductor layer comprising a channel formation region, the oxidesemiconductor layer comprising oxygen and metal elements, the metalelements including indium; a metal oxide layer on and in contact withthe oxide semiconductor layer; an insulating layer comprising siliconand oxygen over the metal oxide layer; and a gate electrode adjacent tothe oxide semiconductor layer, wherein the metal oxide layer comprisesoxygen and at least one of the metal elements of the oxide semiconductorlayer, and wherein the oxide semiconductor layer comprises excessiveoxygen to reduce an amount of oxygen vacancy which is associated with abond between indium and oxygen.
 35. The semiconductor device accordingto claim 34, wherein the metal oxide layer is insulating.
 36. Thesemiconductor device according to claim 34, wherein the gate electrodeis located over the oxide semiconductor layer.
 37. The semiconductordevice according to claim 34, wherein the metal oxide layer comprisesgallium and oxygen.
 38. The semiconductor device according to claim 34,wherein at least part of the metal oxide layer comprises oxygen at aconcentration higher than a stoichiometric ratio in order to reduce anamount of oxygen vacancy which is associated with a bond between indiumand oxygen.
 39. The semiconductor device according to claim 34, whereinat least part of the oxide semiconductor layer comprises oxygen at aconcentration higher than a stoichiometric ratio in order to reduce anamount of oxygen vacancy which is associated with a bond between indiumand oxygen.
 40. A semiconductor device comprising: an oxidesemiconductor layer comprising a channel formation region, the oxidesemiconductor layer comprising oxygen and metal elements, the metalelements including indium; a metal oxide layer on and in contact withthe oxide semiconductor layer; an insulating layer comprising siliconand oxygen over the metal oxide layer; and a gate electrode adjacent tothe oxide semiconductor layer, wherein the metal oxide layer comprisesoxygen and gallium, and wherein the oxide semiconductor layer comprisesexcessive oxygen to reduce an amount of oxygen vacancy which isassociated with a bond between indium and oxygen.
 41. The semiconductordevice according to claim 40, wherein the metal oxide layer isinsulating.
 42. The semiconductor device according to claim 40, whereinthe gate electrode is located over the oxide semiconductor layer. 43.The semiconductor device according to claim 40, wherein at least part ofthe metal oxide layer comprises oxygen at a concentration higher than astoichiometric ratio in order to reduce an amount of oxygen vacancywhich is associated with a bond between indium and oxygen.
 44. Thesemiconductor device according to claim 40, wherein at least part of theoxide semiconductor layer comprises oxygen at a concentration higherthan a stoichiometric ratio in order to reduce an amount of oxygenvacancy which is associated with a bond between indium and oxygen.